Laundry care compositions

ABSTRACT

A laundry care composition comprises a laundry care ingredient or adjunct and at least one compound that is capable of changing from a first color state (i.e., the initial color state in the composition) to a second color state that is perceptibly different from the first color state. A method for treating textile articles comprises the steps of: (a) providing a laundry care composition as described above; (b) adding the laundry care composition to a liquid medium; and (c) placing the textile articles in the liquid medium.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims, pursuant to 35 U.S.C. § 119(e), priority to andthe benefit of the filing date of U.S. Patent Application No.61/989,471, which application was filed on May 6, 2014.

TECHNICAL FIELD OF THE INVENTION

This application describes laundry care compositions and their use inthe laundering of textile articles. More specifically, the applicationdescribes laundry care compositions that are designed to enhance theapparent or visually perceived whiteness of or to impart a desired hueto textile articles washed or otherwise treated with the laundry carecomposition.

BACKGROUND

With repeated wear and laundering, the appearance of textile articlescan begin to deteriorate. This deterioration can become very apparent onwhite textile articles, with the article begin to develop a yellow ordingy appearance. In an effort to reduce or at least slow thisdeterioration, some laundry care compositions have incorporated a bluingor hueing agent. These bluing or hueing agents are colorants that willimpart a slight bluish hue to the textile articles. The resulting bluishhue helps to mask the yellowing of the textile article. Also, a bluishwhite is perceived by many to be whiter or “cleaner” than other shadesof white.

One drawback to the use of bluing or hueing agents is that theytypically are incorporated into the laundry care composition at levelsthat can render the composition a deep, dark blue. And while someconsumers may prefer a laundry care composition exhibiting such a color,other consumers do not prefer these hues.

A need therefore exists for laundry care compositions that exhibitcoloration that is pleasing to a wide variety of consumers and yet iscapable of bluing or hueing textile articles washed or otherwise treatedwith the laundry care composition. The compositions described hereinattempt to provide such benefits.

BRIEF SUMMARY OF THE INVENTION

In a first embodiment, the invention provides a laundry care compositioncomprising a laundry care ingredient or adjunct and at least onecompound that is capable of changing from a first color state (i.e., theinitial color state in the composition) to a second color state that isperceptibly different from the first color state.

In a specific embodiment, the invention provides a laundry carecomposition comprising a laundry care ingredient and at least onecompound conforming to a structure selected from the group consisting ofFormulae (I)-(XC) below

wherein X₁ and X₂ are selected from the group consisting of a carbonatom and a nitrogen atom; a is an integer from 0 to 5, provided a is aninteger from 0 to 4 when one of X₁ and X₂ is a nitrogen atom and a is aninteger from 0 to 3 when both X₁ and X₂ are nitrogen atoms; each R₁ isindependently selected from the group consisting of halogens, a hydroxygroup, a nitro group, alkyl groups, substituted alkyl groups, —S(O)₂OH,—S(O)₂O⁻[M⁺], —C(O)OR₅, —C(O)R₅, —C(O)NR₅R₆, —NC(O)OR₅, —NC(O)SR₅, —OR₅,—NR₅R₆, —S(O)₂R₅, —S(O)₂NR₅R₆, and —P(O)₂R₅; M is a cation; R₅ and R₆are independently selected from the group consisting of hydrogen, alkylgroups, substituted alkyl groups, aryl groups, substituted aryl groups,and R_(a); R₂ and R₃ are independently selected from the groupconsisting of aryl groups, substituted aryl groups, heteroaryl groups,and substituted heteroaryl groups, provided at least one of R₂ and R₃ isheteroaryl group or a substituted heteroaryl group when both X₁ and X₂are carbon atoms; L₁ is selected from the group consisting of hydrogen,halogens, a hydroxy group, a cyano group, and —OR₈; R₈ is selected fromthe group consisting of alkyl groups and substituted alkyl groups;

wherein X₁₀ is selected from the group consisting of —C(O)— and —S(O)₂;d is an integer from 0 to 4; each R₁₀ is independently selected from thegroup consisting of halogens, a nitro group, alkyl groups, substitutedalkyl groups, aryl groups, substituted aryl groups, —S(O)₂OH,—S(O)₂O⁻[M⁺], —C(O)OR₅, —C(O)R₅, —C(O)NR₅R₆, —NC(O)OR₅, —NC(O)SR₅, —OR₅,—NR₅R₆, —S(O)₂R₅, —S(O)₂NR₅R₆, and —P(O)₂R₅; provided at least one of R₂and R₃ is selected from the group consisting of heteroaryl groups andsubstituted heteroaryl groups;

wherein e and f are independently integers from 0 to 4; each R₂₀ and R₂₁is independently selected from the group consisting of halogens, a nitrogroup, alkyl groups, substituted alkyl groups, —NC(O)OR₅, —NC(O)SR₅,—OR₅, and —NR₅R₆; each R₂₅ is independently selected from the groupconsisting of saccharide residues (i.e., monosaccharide residues,disaccharide residues, oligosaccharide residues, and polysaccharideresidues), —C(O)R₅, —C(O)OR₅, —C(O)NR₅R₆; and each R₂₂ and R₂₃ isindependently selected from the group consisting of hydrogen, alkylgroups, and substituted alkyl groups;

wherein R₃₀ is selected from the group consisting of —OR₃₆ and —NR₃₆R₃₇,each R₃₆ and R₃₇ is independently selected from the group consisting ofhydrogen, alkyl groups, substituted alkyl groups, aryl groups,substituted aryl groups, acyl groups, —C(O)OR₅, —C(O)R₅, and —C(O)NR₅R₆;g and h are independently integers from 0 to 4; each R₃₁ and R₃₂ isindependently selected from the group consisting of alkyl groups,substituted alkyl groups, aryl groups, substituted aryl groups,—S(O)₂OH, —S(O)₂O⁻[M⁺], —C(O)OR₅, —C(O)R₅, —C(O)NR₅R₆, —NC(O)OR₅,—NC(O)SR₅, —OR₅, —NR₅R₆, —S(O)₂R₅, —S(O)₂NR₅R₆, and —P(O)₂R₅; R₃₄ andR₃₅ are independently selected from the group consisting of hydrogen,alkyl groups, substituted alkyl groups, aryl groups, substituted arylgroups, and R_(a); R₃₃ is selected from the group consisting ofhydrogen, —S(O)₂R₅, —C(O)N(H)R₅; —C(O)OR₅; and —C(O)R₅; X₃₀, X₃₁, X₃₂,and X₃₃ are independently selected from the group consisting of a carbonatom and a nitrogen atom, provided no more than two of X₃₀, X₃₁, X₃₂,and X₃₃ are nitrogen atoms;

wherein X₄₀ is selected from the group consisting of an oxygen atom, asulfur atom, and NR₄₅; R₄₅ is selected from the group consisting ofalkyl groups, substituted alkyl groups, aryl groups, substituted arylgroups, —S(O)₂OH, —S(O)₂O⁻[M⁺], —C(O)OR₅, —C(O)R₅, and —C(O)NR₅R₆; R₄₀and R₄₁ are independently selected from the group consisting of —OR₅ and—NR₅R₆; j and k are independently integers from 0 to 3; each R₄₂ and R₄₃is independently selected from the group consisting of alkyl groups,substituted alkyl groups, aryl groups, substituted aryl groups,—S(O)₂R₅, —C(O)NR₅R₆, —NC(O)OR₅, —NC(O)SR₅, —C(O)OR₅, —C(O)R₅, —OR₅,—NR₅R₆; R₄₄ is selected from the group consisting of —C(O)R₅,—C(O)NR₅R₆, —C(O)OR₅, and —C(O)OR₅;

wherein R₅₀, R₅₁, and R₅₂ are independently selected from the groupconsisting of aryl groups, substituted aryl groups, heteroaryl groups,and substituted heteroaryl groups; Z is an anion; m and n areindependently positive integers; y is the charge of the anion; thevalues of m, n, and y satisfy the following equation m=(−1)·y·n;

wherein R₅₄ and R₅₅ are independently selected from the group consistingof aryl groups, substituted aryl groups, heteroaryl groups, andsubstituted heteroaryl groups; R₅₃ is selected from the group consistingof arenediyl groups, substituted arenediyl groups, heteroarenediylgroups, and substituted heteroarenediyl groups; p is a positive integer;the values of p, n, and y satisfy the following equation 2m=(−1)·y·n;

wherein X₆₀ is selected from the group consisting of a nitrogen atom anda sulfur atom; X₆₁ is selected from the group consisting of an oxygenatom and a sulfur atom; X₆₂ is selected from the group consisting of acarbon atom and a nitrogen atom; q and r are independently integers from0 to 4; each R₆₀ and R₆₁ is independently selected from the groupconsisting of halogens, alkyl groups, substituted alkyl groups, arylgroups, substituted aryl groups, —OR₅, and —NR₅R₆; if q or r is 2 orgreater, adjacent R₆₀ and R₆₁ groups can be combined to form an arylgroup or a substituted aryl group; R₆₂ is selected from the groupconsisting of alkyl groups and substituted alkyl groups;

wherein X₇₀ is selected from the group consisting of an oxygen atom, anitrogen atom, and a sulfur atom; X₇₁ is selected from the groupconsisting of a carbon atom and a nitrogen atom; s and t areindependently integers from 0 to 4; each R₇₀ and R₇₁ are independentlyselected from the group consisting of halogens, alkyl groups,substituted alkyl groups, aryl groups, substituted aryl groups,—NC(O)OR₅, —NC(O)SR₅, —OR₅, and —NR₅R₆; if s or t is 2 or greater,adjacent R₇₀ and R₇₁ groups can be combined to form an aryl group or asubstituted aryl group;

wherein R₈₀ and R₈₁ are independently selected from the group consistingof alkenyl groups, substituted alkenyl groups, aryl groups, substitutedaryl groups, heteroaryl groups, and substituted heteroaryl groups; R₈₂,R₈₃, R₈₄, and R₈₅ are independently selected from the group consistingof hydrogen, alkyl groups, substituted alkyl groups, aryl groups,substituted aryl groups, —C(O)OR₅, —C(O)R₅, —C(O)NR₅R₆, —NC(O)OR₅,—NC(O)SR₅, —OR₅, and —S(O)₂R₅; further, R₈₂ and R₈₅ can be combined toform a bridging alkanediyl group, a bridging oxygen atom, a bridgingnitrogen atom, or a bridging sulfur atom;

wherein u is an integer from 0 to 3; v and w are independently integersfrom 0 to 4; R₉₀, R₉₁, and R₉₂ are independently selected from the groupconsisting of halogens, alkyl groups, substituted alkyl groups, arylgroups, substituted aryl groups, —OR₅, —NR₅R₆, —C(O)OR₅, —C(O)NR₅R₆,—NC(O)OR₅, —NC(O)SR₅, —S(O)₂R₅, and —S(O)₂NR₅R₆;wherein R_(a) is selected from the group consisting of—R_(x)—O—R_(y)—R_(z) and —R_(y)—R_(z); R_(x) is selected from the groupconsisting of alkanediyl groups and arenediyl groups; R_(z) is selectedfrom the group consisting of hydrogen, alkyl groups, substituted alkylgroups, acyl groups, and R_(b); R_(b) is a monovalent group conformingto a structure selected from the group consisting of Formulae (I)-(XC);and R_(y) is a divalent substituent selected from the group consistingof:

(i) divalent substituents comprising two or more divalent repeatingunits independently selected from repeating units conforming to thestructure of Formula (C)

wherein R₁₀₁ and R₁₀₂ are independently selected from the groupconsisting of hydrogen, alkyl, hydroxyalkyl, aryl, alkoxyalkyl, andaryloxyalkyl;

(ii) divalent substituents conforming to the structure of Formula (CX)

wherein R₁₁₁ and R₁₁₂ are independently selected from the groupconsisting of hydrogen, hydroxyl, and C₁-C₁₀ alkyl, aa is an integerfrom 1 to 12, and bb is an integer greater than or equal to 1 (e.g.,from 1 to 100);

(iii) divalent substituents conforming to the structure of Formula (CXX)

wherein R₁₂₁ and R₁₂₂ are independently selected from the groupconsisting of hydrogen, hydroxyl, and C₁-C₁₀ alkyl, cc is an integerfrom 1 to 12, and dd is an integer greater than or equal to 1 (e.g.,from 1 to 100);

(iv) divalent substituents conforming to the structure of Formula (CXXX)

wherein R₁₃₁, R₁₃₂, and R₁₃₃ are independently selected from alkyl andhydroxyalkyl, and ee is an integer greater than or equal to 1 (e.g.,from 1 to 100);

(v) divalent substituents conforming to the structure of Formula (CXL)

wherein each R₁₄₁ is independently selected from the group consisting ofhydrogen and alkylamine groups, and ff is an integer greater than orequal to 1 (e.g., from 1 to 100);

(vi) divalent substituents conforming to the structure of Formula (CL)

wherein gg is an integer greater than or equal to 1 (e.g., from 1 to100);

(vii) divalent substituents conforming to the structure of Formula (CLX)

wherein each R₁₆₁ is independently selected from the group consisting ofhydrogen and methyl, and hh is an integer greater than or equal to 1(e.g., from 1 to 100);

(viii) divalent substituents conforming to the structure of Formula(CLXX)

wherein each R₁₇₁, R₁₇₂, and R₁₇₃ is independently selected from thegroup consisting of hydrogen and —CH₂CO₂H, and jj is an integer greaterthan or equal to 1 (e.g., from 1 to 100); and

(ix) divalent substituents comprising two or more substituents selectedfrom the group consisting of substituents conforming to a structure ofFormula (C), (CX), (CXX), (CXXX), (CXL), (CL), (CLX), or (CLXX).

In a second embodiment, the invention provides a method for treatingtextile articles. The method comprises the steps of: (a) providing alaundry care composition as described above; (b) adding the laundry carecomposition to a liquid medium; and (c) placing the textile articles inthe liquid medium. The method is preferably performed under conditionssufficient to convert the compound conforming to a structure selectedfrom the group consisting of Formulae (I)-(XC) from the unconjugatedstate represented by the structure to a conjugated state.

DETAILED DESCRIPTION OF THE INVENTION

The following definitions are provided to define several of the termsused throughout this application.

As used herein, the term “substituted alkyl groups” refers to univalentfunctional groups derived from substituted alkanes by removal of ahydrogen atom from a carbon atom of the alkane. In this definition, theterm “substituted alkanes” refers to compounds derived from acyclicunbranched and branched hydrocarbons in which (1) one or more of thehydrogen atoms of the hydrocarbon is replaced with a non-hydrogen atom(e.g., a halogen atom) or a non-alkyl functional group (e.g., a hydroxygroup, aryl group, or heteroaryl group) and/or (2) the carbon-carbonchain of the hydrocarbon is interrupted by an oxygen atom (as in anether), a nitrogen atom (as in an amine), or a sulfur atom (as in asulfide).

As used herein, the term “substituted cycloalkyl groups” refers tounivalent functional groups derived from substituted cycloalkanes byremoval of a hydrogen atom from a carbon atom of the cycloalkane. Inthis definition, the term “substituted cycloalkanes” refers to compoundsderived from saturated monocyclic and polycyclic hydrocarbons (with orwithout side chains) in which (1) one or more of the hydrogen atoms ofthe hydrocarbon is replaced with a non-hydrogen atom (e.g., a halogenatom) or a non-alkyl functional group (e.g., a hydroxy group, arylgroup, or heteroaryl group) and/or (2) the carbon-carbon chain of thehydrocarbon is interrupted by an oxygen atom, a nitrogen atom, or asulfur atom.

As used herein, the term “substituted alkoxy groups” refers to univalentfunctional groups derived from substituted hydroxyalkanes by removal ofa hydrogen atom from a hydroxy group. In this definition, the term“substituted hydroxyalkanes” refers to compounds having one or morehydroxy groups bonded to a substituted alkane, and the term “substitutedalkane” is defined as it is above in the definition of substituted alkylgroups.

As used herein, the term “substituted aryl groups” refers to univalentfunctional groups derived from substituted arenes by removal of ahydrogen atom from a ring carbon atom. In this definition, the term“substituted arenes” refers to compounds derived from monocyclic andpolycyclic aromatic hydrocarbons in which one or more of the hydrogenatoms of the hydrocarbon is replaced with a non-hydrogen atom (e.g., ahalogen atom) or a non-alkyl functional group (e.g., a hydroxy group).

As used herein, the term “substituted heteroaryl groups” refers tounivalent functional groups derived from substituted heteroarenes byremoval of a hydrogen atom from a ring atom. In this definition, theterm “substituted heteroarenes” refers to compounds derived frommonocyclic and polycyclic aromatic hydrocarbons in which (1) one or moreof the hydrogen atoms of the hydrocarbon is replaced with a non-hydrogenatom (e.g., a halogen atom) or a non-alkyl functional group (e.g., ahydroxy group) and (2) at least one methine group (—C═) of thehydrocarbon is replaced by a trivalent heteroatom and/or at least onevinylidene group (—CH═CH—) of the hydrocarbon is replaced by a divalentheteroatom.

As used herein, the term “alkanediyl groups” refers to divalentfunctional groups derived from alkanes by removal of two hydrogen atomsfrom the alkane. These hydrogen atoms can be removed from the samecarbon atom on the alkane (as in ethane-1,1-diyl) or from differentcarbon atoms (as in ethane-1,2-diyl).

As used herein, the term “substituted alkanediyl groups” refers todivalent functional groups derived from substituted alkanes by removalof two hydrogen atoms from the alkane. These hydrogen atoms can beremoved from the same carbon atom on the substituted alkane (as in2-fluoroethane-1,1-diyl) or from different carbon atoms (as in1-fluoroethane-1,2-diyl). In this definition, the term “substitutedalkanes” has the same meaning as set forth above in the definition ofsubstituted alkyl groups.

As used herein, the term “cycloalkanediyl groups” refers to divalentfunctional groups derived from cycloalkanes by removal of two hydrogenatoms from the cycloalkane. These hydrogen atoms can be removed from thesame carbon atom on the cycloalkane or from different carbon atoms.

As used herein, the term “substituted cycloalkanediyl groups” refers todivalent functional groups derived from substituted cycloalkanes byremoval of two hydrogen atoms from the alkane. In this definition, theterm “substituted cycloalkanes” has the same meaning as set forth abovein the definition of substituted cycloalkyl groups.

As used herein, the term “arenediyl groups” refers to divalentfunctional groups derived from arenes (monocyclic and polycyclicaromatic hydrocarbons) by removal of two hydrogen atoms from ring carbonatoms.

As used herein, the term “substituted arenediyl groups” refers todivalent functional groups derived from substituted arenes by removal oftwo hydrogen atoms from ring carbon atoms. In this definition, the term“substituted arenes” refers to compounds derived from monocyclic andpolycyclic aromatic hydrocarbons in which one or more of the hydrogenatoms of the hydrocarbon is replaced with a non-hydrogen atom (e.g., ahalogen atom) or a non-alkyl functional group (e.g., a hydroxy group).

As used herein, the term “heteroarenediyl groups” refers to divalentfunctional groups derived from heteroarenes by removal of two hydrogenatoms from ring atoms. In this definition, the term “heteroarenes”refers to compounds derived from monocyclic and polycyclic aromatichydrocarbons in which at least one methine group (—C═) of thehydrocarbon is replaced by a trivalent heteroatom and/or at least onevinylidene group (—CH═CH—) of the hydrocarbon is replaced by a divalentheteroatom.

As used herein, the term “substituted heteroarenediyl groups” refers todivalent functional groups derived from substituted heteroarenes byremoval of two hydrogen atoms from ring atoms. In this definition, theterm “substituted heteroarenes” has the same meaning as set forth abovein the definition of substituted heteroaryl groups.

As used herein, the term “acyl groups” refers to univalent functionalgroups derived from alkyl carboxylic acids by removal of a hydroxy groupfrom a carboxylic acid group. In this definition, the term “alkylcarboxylic acids” refers to acyclic, unbranched and branchedhydrocarbons having one or more carboxylic acidgroups.

As used herein, the term “substituted acyl groups” refers to univalentfunctional groups derived from substituted alkyl carboxylic acids byremoval of a hydroxy group from a carboxylic acid group. In thisdefinition, the term “substituted alkyl carboxylic acids” refers tocompounds having one or more carboxylic acid groups bonded to asubstituted alkane, and the term “substituted alkane” is defined as itis above in the definition of substituted alkyl groups.

As used herein, the term “laundry care composition” includes, unlessotherwise indicated, granular, powder, liquid, gel, paste, unit dose,bar form and/or flake type washing agents and/or fabric treatmentcompositions, including but not limited to products for launderingfabrics, fabric softening compositions, fabric enhancing compositions,fabric freshening compositions, and other products for the care andmaintenance of fabrics, and combinations thereof. Such compositions maybe pre-treatment compositions for use prior to a washing step or may berinse added compositions, as well as cleaning auxiliaries, such asbleach additives and/or “stain-stick” or pre-treat compositions orsubstrate-laden products, such as dryer added sheets.

As used herein, the term “detergent composition” is a sub-set of laundrycare composition and includes cleaning compositions including but notlimited to products for laundering fabrics. Such compositions may bepre-treatment composition for use prior to a washing step or may berinse added compositions, as well as cleaning auxiliaries, such asbleach additives and “stain-stick” or pre-treat types.

As used herein, “cellulosic substrates” are intended to include anysubstrate which comprises at least a majority by weight of cellulose.Cellulose may be found in wood, cotton, linen, jute, and hemp.Cellulosic substrates may be in the form of powders, fibers, pulp andarticles formed from powders, fibers and pulp. Cellulosic fibers,include, without limitation, cotton, rayon (regenerated cellulose),acetate (cellulose acetate), triacetate (cellulose triacetate), andmixtures thereof. Articles formed from cellulosic fibers include textilearticles such as fabrics. Articles formed from pulp include paper.

As used herein, the term “solid” includes granular, powder, bar andtablet product forms.

As used herein, the term “fluid” includes liquid, gel, paste and gasproduct forms.

Unless otherwise noted, all component or composition levels are inreference to the active portion of that component or composition, andare exclusive of impurities, for example, residual solvents orby-products, which may be present in commercially available sources ofsuch components or compositions.

All percentages and ratios are calculated by weight unless otherwiseindicated. All percentages and ratios are calculated based on the totalcomposition unless otherwise indicated.

In a first embodiment, the invention provides a laundry care compositioncomprising a laundry care ingredient or adjunct and at least onecompound that is capable of changing from a first color state (i.e., theinitial color state in the composition) to a second color state that isperceptibly different from the first color state. Thus, the compound canchange from an uncolored state to a colored state. Alternatively, thecompound can change from a first color to a second color, with the firstcolor and second colors being perceptibly different from each other. Ina preferred embodiment, the second color state of the compound exhibitsa λmax in the wavelength range of about 480 to about 680 nm, morepreferably about 540 to about 680 nm and most preferably about 520 toabout 320 nm. In another preferred embodiment, the first color state ofthe compound is colorless (i.e., the compound does not exhibit avisually perceptible color) and the second color state of the compoundexhibits a λmax in the wavelength range of about 480 to about 680 nm,more preferably about 540 to about 680 nm and most preferably about 520to about 320 nm.

The compound can be any suitable compound capable of exhibiting thecolor change characteristics described above. Preferably, the compoundconforms to a structure selected from the group consisting of Formulae(I), (X), (XX), (XXV), (XXX), (XXXV), (XL), (L), (LV), (LX), (LXX),(LXXX), and (XC) below.

The structure of Formula (I) is

In this structure, X₁ and X₂ are selected from the group consisting of acarbon atom and a nitrogen atom. The variable a is an integer from 0 to5, provided a is an integer from 0 to 4 when one of X₁ and X₂ is anitrogen atom and a is an integer from 0 to 3 when both X₁ and X₂ arenitrogen atoms. Each R₁ is independently selected from the groupconsisting of halogens, a hydroxy group, a nitro group, alkyl groups,substituted alkyl groups, —S(O)₂OH, —S(O)₂O⁻[M⁺], —C(O)OR₅, —C(O)R₅,—C(O)NR₅R₆, —NC(O)OR₅, —NC(O)SR₅, —OR₅, —NR₅R₆, —S(O)₂R₅, —S(O)₂NR₅R₆,and —P(O)₂R₅. Each M is a cation. R₅ and R₆ are independently selectedfrom the group consisting of hydrogen, alkyl groups, substituted alkylgroups, aryl groups, substituted aryl groups, and R_(a). R₂ and R₃ areindependently selected from the group consisting of aryl groups,substituted aryl groups, heteroaryl groups, and substituted heteroarylgroups, provided at least one of R₂ and R₃ preferably is a heteroarylgroup or a substituted heteroaryl group when both X₁ and X₂ are carbonatoms. L₁ is selected from the group consisting of hydrogen, halogens, ahydroxy group, a cyano group, and —OR₈; and R₈ is selected from thegroup consisting of alkyl groups and substituted alkyl groups.

R₂ and R₃ can be any suitable aryl group, substituted aryl group,heteroaryl group, or substituted heteroaryl group. Suitable groupsinclude, but are not limited to, aromatic groups conforming to astructure of Formula (IA)-(IJ) below

In the structures of Formulae (IA)-(IJ), R₅ and R₆ are the same asdefined above, and R₉ is selected from the group consisting of alkylgroups, substituted alkyl groups, aryl groups, substituted aryl groups,heteroaryl groups, substituted heteroaryl groups, a cyano group,halogens, —S(O)₂OH, —S(O)₂NR₅R₆, —C(O)OH, and —C(O)OR₅. Further, two ormore adjacent R₉ groups can be combined to form a fused ring structure.X₃, X₄, X₅, and X₆ are selected from the group consisting of a carbonatom and a nitrogen atom, provided (1) at least one of X₃, X₄, X₅, andX₆ is a nitrogen atom, (2) when X₄ is a nitrogen atom, then X₃ and X₅are both carbon atoms and (3) when X₃ is a nitrogen atom, then X₄ is acarbon atom. The variables za and zb are independently selected from thegroup consisting of integers from 0 to 5, with the sum of za and zbbeing an integer from 0 to 5. The variables zc and zd are independentlyselected from the group consisting of integers from 0 to 3. Thevariables ze and zf are independently selected from the group consistingof integers from 0 to 4, with the sum of ze and zf being less than orequal to 5-N, where N is equal to the number of nitrogen atoms in thearomatic ring. The variables zg and zh are independently selected fromthe group consisting of integers from 0 to 4, with the sum of zg and zhbeing an integer from 0 to 4.

The structure of Formula (X) is

In this structure, X₁₀ is selected from the group consisting of —C(O)—and —S(O)₂. The variable d is an integer from 0 to 4. Each R₁₀ isindependently selected from the group consisting of halogens, a nitrogroup, alkyl groups, substituted alkyl groups, aryl groups, substitutedaryl groups, —S(O)₂OH, —S(O)₂O⁻[M⁺], —C(O)OR₅, —C(O)R₅, —C(O)NR₅R₆,—NC(O)OR₅, —NC(O)SR₅, —OR₅, —NR₅R₆, —S(O)₂R₅, —S(O)₂NR₅R₆, and —P(O)₂R₅.Preferably, at least one of R₂ and R₃ is selected from the groupconsisting of heteroaryl groups and substituted heteroaryl groups. R₅and R₆ are as defined above in the structure of Formula (I).

The structure of Formula (XX) is

The structure of Formula (XXV) is

In these structures, the variables e and f are independently integersfrom 0 to 4. Each R₂₀ and R₂₁ is independently selected from the groupconsisting of halogens, a nitro group, alkyl groups, substituted alkylgroups, —NC(O)OR₅, —NC(O)SR₅, —OR₅, and —NR₅R₆. Each R₂₅ isindependently selected from the group consisting of saccharide residues(i.e., monosaccharide residues, disaccharide residues, oligosaccharideresidues, and polysaccharide residues), —C(O)R₅, —C(O)OR₅, —C(O)NR₅R₆.Each R₂₂ and R₂₃ is independently selected from the group consisting ofhydrogen, alkyl groups, and substituted alkyl groups. R₅ and R₆ are asdefined above in the structure of Formula (I).

The structure of Formula (XXX) is

The structure of Formula (XXXV) is

In these structures, R₃₀ is selected from the group consisting of —OR₃₆and —NR₃₆R₃₇. Each R₃₆ and R₃₇ is independently selected from the groupconsisting of hydrogen, alkyl groups, substituted alkyl groups, arylgroups, substituted aryl groups, acyl groups, —C(O)OR₅, —C(O)R₅, and—C(O)NR₅R₆. The variables g and h are independently integers from 0 to4. Each R₃₁ and R₃₂ is independently selected from the group consistingof alkyl groups, substituted alkyl groups, aryl groups, substituted arylgroups, —S(O)₂OH, —S(O)₂O⁻[M⁺], —C(O)OR₅, —C(O)R₅, —C(O)NR₅R₆,—NC(O)OR₅, —NC(O)SR₅, —OR₅, —NR₅R₆, —S(O)₂R₅, —S(O)₂NR₅R₆, and —P(O)₂R₅.R₃₄ and R₃₅ are independently selected from the group consisting ofhydrogen, alkyl groups, substituted alkyl groups, aryl groups,substituted aryl groups, and R_(a). R₃₃ is selected from the groupconsisting of hydrogen, —S(O)₂R₅, —C(O)N(H)R₅, —C(O)OR₅; and —C(O)R₅.X₃₀, X₃₁, X₃₂, and X₃₃ are independently selected from the groupconsisting of a carbon atom and a nitrogen atom, provided no more thantwo of X₃₀, X₃₁, X₃₂, and X₃₃ are nitrogen atoms. R₅ and R₆ are asdefined above in the structure of Formula (I).

The structure of Formula (XL) is

In this structure, X₄₀ is selected from the group consisting of anoxygen atom, a sulfur atom, and NR₄₅. R₄₅ is selected from the groupconsisting of alkyl groups, substituted alkyl groups, aryl groups,substituted aryl groups, —S(O)₂OH, —S(O)₂O⁻[M⁺], —C(O)OR₅, —C(O)R₅, and—C(O)NR₅R₆. R₄₀ and R₄₁ are independently selected from the groupconsisting of —OR₅ and —NR₅R₆. The variables j and k are independentlyintegers from 0 to 3. Each R₄₂ and R₄₃ is independently selected fromthe group consisting of alkyl groups, substituted alkyl groups, arylgroups, substituted aryl groups, —S(O)₂R₅, —C(O)NR₅R₆, —NC(O)OR₅,—NC(O)SR₅, —C(O)OR₅, —C(O)R₅, —OR₅, —NR₅R₆; R₄₄ is selected from thegroup consisting of —C(O)R₅, —C(O)NR₅R₆, —C(O)OR₅, and —C(O)OR₅. R₅ andR₆ are as defined above in the structure of Formula (I).

In a preferred embodiment, R₄₄ is selected from the group consisting of

The structure of Formula (L) is

In this structure, R₅₀, R₅₁, and R₅₂ are independently selected from thegroup consisting of aryl groups, substituted aryl groups, heteroarylgroups, and substituted heteroaryl groups. Z is an anion. The variablesm and n are independently positive integers. The variable y is thecharge of the anion; and the values of m, n, and y satisfy the followingequation m=(−1)·y·n.

The structure of Formula (LV) is

In this structure, R₅₄ and R₅₅ are independently selected from the groupconsisting of aryl groups, substituted aryl groups, heteroaryl groups,and substituted heteroaryl groups. R₅₃ is selected from the groupconsisting of arenediyl groups, substituted arenediyl groups,heteroarenediyl groups, and substituted heteroarenediyl groups. Thevariable p is a positive integer; and the values of p, n, and y satisfythe following equation 2m=(−1)·y·n. R₅₁ and R₅₂ are as defined above inthe structure of Formula (L).

The aromatic groups R₅₀, R₅₁, R₅₂, R₅₄, and R₅₅ of Formula (L) and (LV)can be any suitable aromatic groups. Suitable aromatic groups include,but are not limited to, groups conforming to the structures of Formulae(IA)-(IJ) described above. Suitable divalent aromatic groups for R₅₃include, but are not limited to, divalent analogues of the structures ofFormulae (IA)-(IJ).

The structure of Formula (LX) is

In this structure, X₆₀ is selected from the group consisting of anitrogen atom and a sulfur atom. X₆₁ is selected from the groupconsisting of an oxygen atom and a sulfur atom. X₆₂ is selected from thegroup consisting of a carbon atom and a nitrogen atom. The variables qand r are independently integers from 0 to 4. Each R₆₀ and R₆₁ isindependently selected from the group consisting of halogens, alkylgroups, substituted alkyl groups, aryl groups, substituted aryl groups,—NC(O)OR₅, —NC(O)SR₅, —OR₅, and —NR₅R₆. Further, if q or r is 2 orgreater, adjacent R₆₀ and R₆₁ groups can be combined to form an arylgroup or a substituted aryl group. R₆₂ is selected from the groupconsisting of alkyl groups and substituted alkyl groups. R₅ and R₆ areas defined above in the structure of Formula (I).

The structure of Formula (LXX) is

In this structure, X₇₀ is selected from the group consisting of anoxygen atom, a nitrogen atom, and a sulfur atom. X₇₁ is selected fromthe group consisting of a carbon atom and a nitrogen atom. The variabless and t are independently integers from 0 to 4. Each R₇₀ and R₇₁ areindependently selected from the group consisting of halogens, alkylgroups, substituted alkyl groups, aryl groups, substituted aryl groups,—NC(O)OR₅, —NC(O)SR₅, —OR₅, and —NR₅R₆. Further, if s or t is 2 orgreater, adjacent R₇₀ and R₇₁ groups can be combined to form an arylgroup or a substituted aryl group. R₅ and R₆ are as defined above in thestructure of Formula (I).

The structure of Formula (LXXX) is

In this structure, R₈₀ and R₈₁ are independently selected from the groupconsisting of alkenyl groups, substituted alkenyl groups, aryl groups,substituted aryl groups, heteroaryl groups, and substituted heteroarylgroups. R₈₂, R₈₃, R₈₄, and R₈₅ are independently selected from the groupconsisting of hydrogen, alkyl groups, substituted alkyl groups, arylgroups, substituted aryl groups, —C(O)OR₅, —C(O)R₅, —C(O)NR₅R₆,—NC(O)OR₅, —NC(O)SR₅, —OR₅, and —S(O)₂R₅. Further, R₈₂ and R₈₅ can becombined to form a bridging alkanediyl group, a bridging oxygen atom, abridging nitrogen atom, or a bridging sulfur atom. R₅ and R₆ are asdefined above in the structure of Formula (I).

The aromatic groups R₈₀ and R₈₁ can be any suitable aromatic groups.Suitable aromatic groups include, but are not limited to, groupsconforming to the structures of Formulae (IA)-(IJ) described above.

The structure of Formula (XC) is

In this structure, the variable u is an integer from 0 to 3. Thevariables v and w are independently integers from 0 to 4. R₉₀, R₉₁, andR₉₂ are independently selected from the group consisting of halogens,alkyl groups, substituted alkyl groups, aryl groups, substituted arylgroups, —OR₅, —NR₅R₆, —C(O)OR₅, —C(O)NR₅R₆, —NC(O)OR₅, —NC(O)SR₅,—S(O)₂R₅, and —S(O)₂NR₅R₆. R₅ and R₆ are as defined above in thestructure of Formula (I).

In the structures of Formulae (I), (X), (XX), (XXV), (XXX), (XXXV),(XL), (L), (LV), (LX), (LXX), (LXXX), and (XC), R_(a) is selected fromthe group consisting of —R_(x)—O—R_(y)—R_(z) and —R_(y)—R_(z). R_(x) isselected from the group consisting of alkanediyl groups and arenediylgroups. R_(z) is selected from the group consisting of hydrogen, alkylgroups, substituted alkyl groups, acyl groups, and R_(b). R_(b) is amonovalent group corresponding to the chromogenic moiety of a structureselected from the group consisting of Formulae (I)-(XC), which meansthat the —R_(x)—O—R_(y)— or —R_(y)— moiety serves a bridge or linkerbetween two chromogenic moieties. R_(y) is a divalent substituentselected from the group consisting of:

(i) divalent substituents comprising two or more divalent repeatingunits independently selected from repeating units conforming to thestructure of Formula (C)

wherein R₁₀₁ and R₁₀₂ are independently selected from the groupconsisting of hydrogen, alkyl, hydroxyalkyl, aryl, alkoxyalkyl, andaryloxyalkyl;

(ii) divalent substituents conforming to the structure of Formula (CX)

wherein R₁₁₁ and R₁₁₂ are independently selected from the groupconsisting of hydrogen, hydroxyl, and C₁-C₁₀ alkyl, aa is an integerfrom 1 to 12, and bb is an integer greater than or equal to 1 (e.g.,from 1 to 100);

(iii) divalent substituents conforming to the structure of Formula (CXX)

wherein R₁₂₁ and R₁₂₂ are independently selected from the groupconsisting of hydrogen, hydroxyl, and C₁-C₁₀ alkyl, cc is an integerfrom 1 to 12, and dd is an integer greater than or equal to 1 (e.g.,from 1 to 100);

(iv) divalent substituents conforming to the structure of Formula (CXXX)

wherein R₁₃₁, R₁₃₂, and R₁₃₃ are independently selected from alkyl andhydroxyalkyl, and ee is an integer greater than or equal to 1 (e.g.,from 1 to 100);

(v) divalent substituents conforming to the structure of Formula (CXL)

wherein each R₁₄₁ is independently selected from the group consisting ofhydrogen and alkylamine groups, and ff is an integer greater than orequal to 1 (e.g., from 1 to 100);

(vi) divalent substituents conforming to the structure of Formula (CL)

wherein gg is an integer greater than or equal to 1 (e.g., from 1 to100);

(vii) divalent substituents conforming to the structure of Formula (CLX)

wherein each R₁₆₁ is independently selected from the group consisting ofhydrogen and methyl, and hh is an integer greater than or equal to 1(e.g., from 1 to 100);

(viii) divalent substituents conforming to the structure of Formula(CLXX)

wherein each R₁₇₁, R₁₇₂, and R₁₇₃ is independently selected from thegroup consisting of hydrogen and —CH₂CO₂H, and jj is an integer greaterthan or equal to 1 (e.g., from 1 to 100); and

(ix) divalent substituents comprising two or more substituents selectedfrom the group consisting of substituents conforming to a structure ofFormula (C), (CX), (CXX), (CXXX), (CXL), (CL), (CLX), or (CLXX).

In a series of preferred embodiments, R^(y) is a divalent substituentconforming to a structure selected from the group consisting of Formulae(CA), (CB), and (CC)

In the structures of Formulae (CA), (CB), and (CC), ff, gg, and hh areselected from the group consisting of zero and positive integers (e.g.,integers from 0 to about 100); and the sum of s, t, and v is 2 or more(e.g., 2 to about 300, 3 to about 300, 2 to about 200, 3 to about 200, 2to about 100, 3 to about 100, 2 to about 50, 3 to about 50, about 3 toabout 30, about 3 to about 25, or about 3 to about 20).

In the structures of Formulae (CA), (CB), and (CC), the divalentsubstituent R^(y) is depicted as comprising a series of repeating unitsarranged in a block configuration. While such an arrangement of therepeating units is possible and potentially preferred, the repeatingunits comprising the divalent substituent R^(y) can also be arranged ina random configuration or in any suitable combination of a blockconfiguration and a random configuration. For example, R^(y) can be adivalent substituent comprising a series of two or more differentrepeating units conforming to the structure of Formula (CA) arranged ina random configuration or a divalent substituent comprising a series oftwo more different repeating units conforming to the structure ofFormula (CA) and one or more repeating units conforming to the structureof Formula (CB) all arranged in a random configuration. Also, R^(y) canbe a divalent substituent comprising a series of two or more differentrepeating units conforming to the structure of Formula (CA) arranged ina random configuration followed by a block of repeating units conformingto the structure of Formula (CB).

As can be seen from the structures of Formulae (I), (X), (XX), (XXV),(XXX), (XXXV), (XL), (L), (LV), (LX), (LXX), (LXXX), and (XC), eachcompound possesses a structure in which a conjugated system (i.e., asystem of conjugated p-orbitals) is interrupted by the presence of anadditional substituent. For example, in the structure of Formula (I),the L group interrupts a conjugated system that would otherwise beformed by the aryl/heteroaryl groups surrounding the central carbonatom. This interruption of the conjugated system limits the compound'sabsorption of electromagnetic radiation in the visible spectrum andcauses the compound to exhibit a first color state. Indeed, if theconjugation is very limited, the compound may not exhibit anyperceptible absorption in the visible spectrum, meaning that thecompound would be colorless. However, once the substituent interruptingthe conjugation is removed, the compound possesses a conjugated system.And the compound will then exhibit a second color state due to thepresence of this conjugated system.

The structures below depict the conjugated equivalents to the compoundsof Formulae (I), (X), (XX), (XXV), (XXX), (XXXV), (XL), (L), (LV), (LX),(LXX), (LXXX), and (XC). The conjugated equivalent bears a similar labelto the compounds above but is additionally designated with a prime (′)symbol.

The substituent interrupting the conjugation can be removed or releasedby any suitable means. For example, the substituent can be released whenthe compound is exposed to a different pH. This may occur, for instance,when the pH changes from the basic conditions of the laundry carecomposition to the relatively pH neutral conditions of the wash water.The change may also be triggered by a change in temperature (i.e., achange from the ambient temperature of the laundry care composition tothe temperature of the wash water or exposure to heat in the dryer). Thechange can also be triggered by a change in the solvent in which thecompound is contained (e.g., the compound can exhibit solvatochromism),such as change from the environment of the laundry care composition tothe wash water/liquor. Alternatively, the change may be triggered byexposure of the compound to light. The change may also be triggered by aredox reaction that occurs due to a change in the redox environment inwhich the compound exists. For example, the compound can be maintainedin the first color state by the presence of a reducing agent. When thereducing agent is washed away during the wash cycle, the compound canthen undergo an oxidation reaction to yield the conjugated form of thecompound and change to the second color state. The color change can betriggered by the action of an enzyme that is contained in thecomposition and acts to cleave the bond to the group that is interruptedthe conjugation in the compound. For certain groups of the compound(such as the compounds conforming to the structures of Formulae (X) and(XC)), the color change can be triggered by a developing agent, such asa Lewis acid, a quaternary salt, or a Brønsted acid. The compound or theagent that triggers the color change (e.g., developing agent or enzyme)can also be encapsulated in order to isolate the two when thecomposition is being stored. In such an embodiment, the capsulecontaining the compound or triggering agent would be designed to breakand release its contents at the appropriate point in the use of thecomposition. The change may also be triggered when the compound chelatescharged ions (e.g., Mg²⁺ or Ca²⁺) present in the wash water. Dependingon the particular compound that is used, each of the mechanismsdescribed above can alone trigger the change, or two or more mechanismscan jointly trigger the change. For example, the change to theconjugated form can be triggered by the changes in both pH andtemperature that occur when the laundry care composition is added to thewash water.

The compound can be present in the laundry care composition in anysuitable amount. For example, the compound conforming to a structureselected from the group consisting of Formulae (I)-(XC) can be presentin the laundry care composition in an amount of about 0.001 wt. % ormore. The compound typically is present in the laundry care compositionin an amount of about 20 wt. % or less. Thus, in a preferred embodiment,the compound conforming to a structure selected from the groupconsisting of Formulae (I)-(XC) is present in the laundry carecomposition in an amount of about 0.001 wt. % to about 20 wt. %.

Laundry Care Adjunct Materials.

Suitable adjuncts may be, for example to assist or enhance cleaningperformance, for treatment of the substrate to be cleaned, for exampleby softening or freshening, or to modify the aesthetics of thecomposition as is the case with perfumes, colorants, non-fabric-shadingdyes or the like. Suitable adjunct materials include, but are notlimited to, surfactants, builders, chelating agents, dye transferinhibiting agents, dispersants, enzymes, and enzyme stabilizers,catalytic materials, bleach activators, hydrogen peroxide, sources ofhydrogen peroxide, preformed peracids, polymeric dispersing agents, claysoil removal/anti-redeposition agents, brighteners, suds suppressors,dyes, hueing dyes, perfumes, perfume delivery systems, structureelasticizing agents, fabric softeners, carriers, hydrotropes, processingaids, solvents, additional dyes and/or pigments, some of which arediscussed in more detail below. In addition to the disclosure below,suitable examples of such other adjuncts and levels of use are found inU.S. Pat. Nos. 5,576,282, 6,306,812 B1 and 6,326,348 B1 that areincorporated by reference.

Additional Fabric Hueing Agents. Although it is not preferred toincorporate additional fabric shading dyes, in addition to the compoundconforming to a structure of Formula (I)-(XC), the composition maycomprise one or more additional fabric hueing agents. Suitable fabrichueing agents include dyes, dye-clay conjugates, and pigments. Suitabledyes include those that deposit more onto cotton textiles compared todeposition onto synthetic textiles such as polyester and/or nylon.Further suitable dyes include those that deposit more onto syntheticfibres such as polyester and/or nylon compared to cotton. Suitable dyesinclude small molecule dyes and polymeric dyes. Suitable small moleculedyes include small molecule dyes selected from the group consisting ofdyes falling into the Color Index (C.I.) classifications of Direct Blue,Direct Red, Direct Violet, Acid Blue, Acid Red, Acid Violet, Basic Blue,Basic Violet and Basic Red, or mixtures thereof. Examples of smallmolecule dyes include those selected from the group consisting of ColorIndex (Society of Dyers and Colourists, Bradford, UK) numbers DirectViolet 9, Direct Violet 35, Direct Violet 48, Direct Violet 51, DirectViolet 66, Direct Violet 99, Direct Blue 1, Direct Blue 71, Direct Blue80, Direct Blue 279, Acid Red 17, Acid Red 73, Acid Red 88, Acid Red150, Acid Violet 15, Acid Violet 17, Acid Violet 24, Acid Violet 43,Acid Red 52, Acid Violet 49, Acid Violet 50, Acid Blue 15, Acid Blue 17,Acid Blue 25, Acid Blue 29, Acid Blue 40, Acid Blue 45, Acid Blue 75,Acid Blue 80, Acid Blue 83, Acid Blue 90 and Acid Blue 113, Acid Black1, Basic Violet 1, Basic Violet 3, Basic Violet 4, Basic Violet 10,Basic Violet 35, Basic Blue 3, Basic Blue 16, Basic Blue 22, Basic Blue47, Basic Blue 66, Basic Blue 75, Basic Blue 159, small molecule dyesselected from the group consisting of Color Index (Society of Dyers andColourists, Bradford, UK) numbers Acid Violet 17, Acid Violet 43, AcidRed 52, Acid Red 73, Acid Red 88, Acid Red 150, Acid Blue 25, Acid Blue29, Acid Blue 45, Acid Blue 113, Acid Black 1, Direct Blue 1, DirectBlue 71. Direct Violet small molecule dyes may be preferred. Dyesselected from the group consisting Acid Violet 17, Direct Blue 71,Direct Violet 51, Direct Blue 1, Acid Red 88, Acid Red 150, Acid Blue29, Acid Blue 113 and mixtures thereof may be preferred.

Suitable polymeric dyes include polymeric dyes selected from the groupconsisting of polymers containing covalently bound chromogens(dye-polymer conjugates) and polymers with chromogens co-polymerizedinto the backbone of the polymer and mixtures thereof, and polymericdyes selected from the group consisting of fabric-substantive colorantssold under the name of Liquitint® (Milliken, Spartanburg, S.C., USA),dye-polymer conjugates formed from at least one reactive dye and apolymer selected from the group consisting of polymers comprising amoiety selected from the group consisting of a hydroxyl moiety, aprimary amine moiety, a secondary amine moiety, a thiol moiety andmixtures thereof. In still another aspect, suitable polymeric dyesinclude polymeric dyes selected from the group consisting of Liquitint®(Milliken, Spartanburg, S.C., USA) Violet CT, carboxymethyl cellulose(CMC) conjugated with a reactive blue, reactive violet or reactive reddye such as CMC conjugated with C.I. Reactive Blue 19, sold by Megazyme,Wicklow, Ireland under the product name AZO-CM-CELLULOSE, product codeS-ACMC, alkoxylated triphenyl-methane polymeric colourants, alkoxylatedthiophene polymeric colourants, and mixtures thereof. Preferredadditional hueing dyes include the whitening agents found in WO 08/87497A1. These whitening agents may be characterized by the followingstructure (M):

wherein R¹ and R² can independently be selected from:a) [(CH₂CR′HO)_(x)(CH₂CR″HO)_(y)H], wherein R′ is selected from thegroup consisting of H, CH₃, CH₂O(CH₂CH₂O)_(z)H, and mixtures thereof;wherein R″ is selected from the group consisting of H,CH₂O(CH₂CH₂O)_(z)H, and mixtures thereof; wherein x+y≤5; wherein y≥1;and wherein z=0 to 5;b) R¹=alkyl, aryl or aryl alkyl and R²=[(CH₂CR′HO)_(x)(CH₂CR″HO)_(y)H]wherein R′ is selected from the group consisting of H, CH₃,CH₂O(CH₂CH₂O)_(z)H, and mixtures thereof; wherein R″ is selected fromthe group consisting of H, CH₂O(CH₂CH₂O)_(z)H, and mixtures thereof;wherein x+y≤10; wherein y≥1; and wherein z=0 to 5;c) R¹=[CH₂CH(OR³)CH₂OR₄] and R²=[CH₂CH(OR₃)CH₂O R⁴]wherein R³ is selected from the group consisting of H, (CH₂CH₂O)_(z)H,and mixtures thereof; and wherein z=0 to 10;wherein R⁴ is selected from the group consisting of (C₁-C₁₆)alkyl, arylgroups, and mixtures thereof; andd) wherein R¹ and R² can independently be selected from the aminoaddition product of styrene oxide, glycidyl methyl ether, isobutylglycidyl ether, isopropylglycidyl ether, t-butyl glycidyl ether,2-ethylhexylgycidyl ether, and glycidylhexadecyl ether, followed by theaddition of from 1 to 10 alkylene oxide units.

A preferred additional fabric hueing agent which may be incorporatedinto the compositions of the invention may be characterized by thefollowing structure (Ml):

wherein R′ is selected from the group consisting of H, CH₃,CH₂O(CH₂CH₂O)_(z)H, and mixtures thereof; wherein R″ is selected fromthe group consisting of H, CH₂O(CH₂CH₂O)_(z)H, and mixtures thereof;wherein x+y≤5; wherein y≥1; and wherein z=0 to 5.

A further preferred additional hueing dye may be characterized by thefollowing structure (MII):

This dye is typically a mixture of compounds having an average of 3-10EO groups, preferably 5 EO groups per molecule.

Further additional shading dyes are those described in USPN 2008 34511A1 (Unilever). A preferred agent is “Solvent Violet 13”.

Suitable dye clay conjugates include dye clay conjugates selected fromthe group comprising at least one cationic/basic dye and a smectiteclay, and mixtures thereof. In another aspect, suitable dye clayconjugates include dye clay conjugates selected from the groupconsisting of one cationic/basic dye selected from the group consistingof C.I. Basic Yellow 1 through 108, C.I. Basic Orange 1 through 69, C.I.Basic Red 1 through 118, C.I. Basic Violet 1 through 51, C.I. Basic Blue1 through 164, C.I. Basic Green 1 through 14, C.I. Basic Brown 1 through23, CI Basic Black 1 through 11, and a clay selected from the groupconsisting of Montmorillonite clay, Hectorite clay, Saponite clay andmixtures thereof. In still another aspect, suitable dye clay conjugatesinclude dye clay conjugates selected from the group consisting of:Montmorillonite Basic Blue B7 C.I. 42595 conjugate, MontmorilloniteBasic Blue B9 C.I. 52015 conjugate, Montmorillonite Basic Violet V3 C.I.42555 conjugate, Montmorillonite Basic Green G1 C.I. 42040 conjugate,Montmorillonite Basic Red R1 C.I. 45160 conjugate, Montmorillonite C.I.Basic Black 2 conjugate, Hectorite Basic Blue B7 C.I. 42595 conjugate,Hectorite Basic Blue B9 C.I. 52015 conjugate, Hectorite Basic Violet V3C.I. 42555 conjugate, Hectorite Basic Green G1 C.I. 42040 conjugate,Hectorite Basic Red R1 C.I. 45160 conjugate, Hectorite C.I. Basic Black2 conjugate, Saponite Basic Blue B7 C.I. 42595 conjugate, Saponite BasicBlue B9 C.I. 52015 conjugate, Saponite Basic Violet V3 C.I. 42555conjugate, Saponite Basic Green G1 C.I. 42040 conjugate, Saponite BasicRed R1 C.I. 45160 conjugate, Saponite C.I. Basic Black 2 conjugate andmixtures thereof.

Suitable pigments include pigments selected from the group consisting offlavanthrone, indanthrone, chlorinated indanthrone containing from 1 to4 chlorine atoms, pyranthrone, dichloropyranthrone,monobromodichloropyranthrone, dibromodichloropyranthrone,tetrabromopyranthrone, perylene-3,4,9,10-tetracarboxylic acid diimide,wherein the imide groups may be unsubstituted or substituted byC₁-C₃-alkyl or a phenyl or heterocyclic radical, and wherein the phenyland heterocyclic radicals may additionally carry substituents which donot confer solubility in water, anthrapyrimidinecarboxylic acid amides,violanthrone, isoviolanthrone, dioxazine pigments, copper phthalocyaninewhich may contain up to 2 chlorine atoms per molecule, polychloro-copperphthalocyanine or polybromochloro-copper phthalocyanine containing up to14 bromine atoms per molecule and mixtures thereof. Particularlypreferred are Pigment Blues 15 to 20, especially Pigment Blue 15 and/or16. Other suitable pigments include those selected from the groupconsisting of Ultramarine Blue (C.I. Pigment Blue 29), UltramarineViolet (C.I. Pigment Violet 15) and mixtures thereof. Suitable hueingagents are described in more detail in U.S. Pat. No. 7,208,459 B2, WO2012/054835, WO 2009/069077, WO 2012/166768.

Encapsulates.

The composition may comprise an encapsulate. In one aspect, anencapsulate comprising a core, a shell having an inner and outersurface, said shell encapsulating said core. The core may comprise anylaundry care adjunct, though typically the core may comprise materialselected from the group consisting of perfumes; brighteners; dyes;insect repellants; silicones; waxes; flavors; vitamins; fabric softeningagents; skin care agents in one aspect, paraffins; enzymes;anti-bacterial agents; bleaches; sensates; and mixtures thereof; andsaid shell may comprise a material selected from the group consisting ofpolyethylenes; polyamides; polyvinylalcohols, optionally containingother co-monomers; polystyrenes; polyisoprenes; polycarbonates;polyesters; polyacrylates; aminoplasts, in one aspect said aminoplastmay comprise a polyurea, polyurethane, and/or polyureaurethane, in oneaspect said polyurea may comprise polyoxymethyleneurea and/or melamineformaldehyde; polyolefins; polysaccharides, in one aspect saidpolysaccharide may comprise alginate and/or chitosan; gelatin; shellac;epoxy resins; vinyl polymers; water insoluble inorganics; silicone; andmixtures thereof. Preferred encapsulates comprise perfume. Preferredencapsulates comprise a shell which may comprise melamine formaldehydeand/or cross linked melamine formaldehyde. Preferred encapsulatescomprise a core material and a shell, said shell at least partiallysurrounding said core material, is disclosed. At least 75%, 85% or even90% of said encapsulates may have a fracture strength of from 0.2 MPa to10 MPa, and a benefit agent leakage of from 0% to 20%, or even less than10% or 5% based on total initial encapsulated benefit agent. Preferredare those in which at least 75%, 85% or even 90% of said encapsulatesmay have (i) a particle size of from 1 microns to 80 microns, 5 micronsto 60 microns, from 10 microns to 50 microns, or even from 15 microns to40 microns, and/or (ii) at least 75%, 85% or even 90% of saidencapsulates may have a particle wall thickness of from 30 nm to 250 nm,from 80 nm to 180 nm, or even from 100 nm to 160 nm. Formaldehydescavengers may be employed with the encapsulates, for example, in acapsule slurry and/or added to a composition before, during or after theencapsulates are added to such composition. Suitable capsules that canbe made by following the teaching of U.S. Patent Application PublicationNo. 2008/0305982 A1; and/or U.S. Patent Application Publication No.2009/0247449 A1. Alternatively, suitable capsules can be purchased fromAppleton Papers Inc. of Appleton, Wis. USA.

In a preferred aspect the composition may comprise a deposition aid,preferably in addition to encapsulates. Preferred deposition aids areselected from the group consisting of cationic and nonionic polymers.Suitable polymers include cationic starches, cationichydroxyethylcellulose, polyvinylformaldehyde, locust bean gum, mannans,xyloglucans, tamarind gum, polyethyleneterephthalate and polymerscontaining dimethylaminoethyl methacrylate, optionally with one or moremonomers selected from the group comprising acrylic acid and acrylamide.

Perfume.

Preferred compositions of the invention comprise perfume. Typically thecomposition comprises a perfume that comprises one or more perfume rawmaterials, selected from the group as described in WO08/87497. However,any perfume useful in a laundry care composition may be used. Apreferred method of incorporating perfume into the compositions of theinvention is via an encapsulated perfume particle comprising either awater-soluble hydroxylic compound or melamine-formaldehyde or modifiedpolyvinyl alcohol. In one aspect the encapsulate comprises (a) an atleast partially water-soluble solid matrix comprising one or morewater-soluble hydroxylic compounds, preferably starch; and (b) a perfumeoil encapsulated by the solid matrix. In a further aspect the perfumemay be pre-complexed with a polyamine, preferably a polyethylenimine soas to form a Schiff base.

Polymers.

The composition may comprise one or more polymers. Examples areoptionally modified carboxymethylcellulose, poly(vinyl-pyrrolidone),poly(ethylene glycol), poly(vinyl alcohol), poly(vinylpyridine-N-oxide),poly(vinylimidazole), polycarboxylates such as polyacrylates,maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acidco-polymers.

The composition may comprise one or more amphiphilic cleaning polymerssuch as the compound having the following general structure:bis((C₂H₅O)(C₂H₄O)n)(CH₃)—N⁺—C_(x)H_(2x)—N⁺—(CH₃)-bis((C₂H₅O)(C₂H₄O)n),wherein n=from 20 to 30, and x=from 3 to 8, or sulphated or sulphonatedvariants thereof. In one aspect, this polymer is sulphated orsulphonated to provide a zwitterionic soil suspension polymer.

The composition preferably comprises amphiphilic alkoxylated greasecleaning polymers which have balanced hydrophilic and hydrophobicproperties such that they remove grease particles from fabrics andsurfaces. Preferred amphiphilic alkoxylated grease cleaning polymerscomprise a core structure and a plurality of alkoxylate groups attachedto that core structure. These may comprise alkoxylatedpolyalkylenimines, preferably having an inner polyethylene oxide blockand an outer polypropylene oxide block. Typically these may beincorporated into the compositions of the invention in amounts of from0.005 to 10 wt. %, generally from 0.5 to 8 wt. %.

Alkoxylated polycarboxylates such as those prepared from polyacrylatesare useful herein to provide additional grease removal performance. Suchmaterials are described in WO 91/08281 and WO 90/01815. Chemically,these materials comprise polyacrylates having one ethoxy side-chain perevery 7-8 acrylate units. The side-chains are of the formula—(CH₂CH₂O)_(m)(CH₂)_(n)CH₃ wherein m is 2-3 and n is 6-12. Theside-chains are ester-linked to the polyacrylate “backbone” to provide a“comb” polymer type structure. The molecular weight can vary, but istypically in the range of about 2000 to about 50,000. Such alkoxylatedpolycarboxylates can comprise from about 0.05% to about 10%, by weight,of the compositions herein.

Mixtures of cosurfactants and other adjunct ingredients, areparticularly suited to be used with an amphiphilic graft co-polymer.Preferred amphiphilic graft co-polymer(s) comprise (i) polyethyeleneglycol backbone; and (ii) and at least one pendant moiety selected frompolyvinyl acetate, polyvinyl alcohol and mixtures thereof. A preferredamphiphilic graft co-polymer is Sokalan HP22, supplied from BASF.Suitable polymers include random graft copolymers, preferably apolyvinyl acetate grafted polyethylene oxide copolymer having apolyethylene oxide backbone and multiple polyvinyl acetate side chains.The molecular weight of the polyethylene oxide backbone is preferablyabout 6000 and the weight ratio of the polyethylene oxide to polyvinylacetate is about 40 to 60 and no more than 1 grafting point per 50ethylene oxide units. Typically these are incorporated into thecompositions of the invention in amounts from 0.005 to 10 wt. %, moreusually from 0.05 to 8 wt. %. Preferably the composition comprises oneor more carboxylate polymer, such as a maleate/acrylate random copolymeror polyacrylate homopolymer. In one aspect, the carboxylate polymer is apolyacrylate homopolymer having a molecular weight of from 4,000 Da to9,000 Da, or from 6,000 Da to 9,000 Da. Typically these are incorporatedinto the compositions of the invention in amounts from 0.005 to 10 wt.%, or from 0.05 to 8 wt. %.

Preferably the composition comprises one or more soil release polymers.Examples include soil release polymers having a structure as defined byone of the following Formulae (MXI), (MXII) or (MXIII):—[(OCHR¹⁰—CHR¹¹)_(a)—O—(O)C—Ar—C(O)—]_(d)  (MXI)—[(OCHR¹²—CHR¹³)_(b)—O—OC-sAr—CO—]_(e)  (MXII)—[(OCHR¹⁴—CHR¹⁵)_(c)—OR¹⁶]_(f)  (MXIII)wherein:a, b and c are from 1 to 200;d, e and f are from 1 to 50;Ar is a 1,4-substituted phenylene;sAr is 1,3-substituted phenylene substituted in position 5 with SO₃Me;Me is Li, K, Mg/2, Ca/2, Al/3, ammonium, mono-, di-, tri-, ortetraalkylammonium wherein the alkyl groups are C₁-C₁₈ alkyl or C₂-C₁₀hydroxyalkyl, or mixtures thereof;R¹⁰, R¹¹, R¹², R¹³, R¹⁴ and R¹⁵ are independently selected from H orC₁-C₁₈ n- or iso-alkyl; andR¹⁶ is a linear or branched C₁-C₁₈ alkyl, or a linear or branched C₂-C₃₀alkenyl, or a cycloalkyl group with 5 to 9 carbon atoms, or a C₈-C₃₀aryl group, or a C₆-C₃₀ arylalkyl group.

Suitable soil release polymers are polyester soil release polymers suchas Repel-o-tex polymers, including Repel-o-tex SF, SF-2 and SRP6supplied by Rhodia. Other suitable soil release polymers include Texcarepolymers, including Texcare SRA100, SRA300, SRN100, SRN170, SRN240,SRN300 and SRN325 supplied by Clariant. Other suitable soil releasepolymers are Marloquest polymers, such as Marloquest SL supplied bySasol.

Preferably the composition comprises one or more cellulosic polymer,including those selected from alkyl cellulose, alkyl alkoxyalkylcellulose, carboxyalkyl cellulose, alkyl carboxyalkyl cellulose.Preferred cellulosic polymers are selected from the group comprisingcarboxymethyl cellulose, methyl cellulose, methyl hydroxyethylcellulose, methyl carboxymethyl cellulose, and mixtures thereof. In oneaspect, the carboxymethyl cellulose has a degree of carboxymethylsubstitution from 0.5 to 0.9 and a molecular weight from 100,000 Da to300,000 Da.

Enzymes.

Preferably the composition comprises one or more enzymes. Preferredenzymes provide cleaning performance and/or fabric care benefits.Examples of suitable enzymes include, but are not limited to,hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases,phospholipases, esterases, cutinases, pectinases, mannanases, pectatelyases, keratinases, reductases, oxidases, phenoloxidases,lipoxygenases, ligninases, pullulanases, tannases, pentosanases,malanases, β-glucanases, arabinosidases, hyaluronidase, chondroitinase,laccase, and amylases, or mixtures thereof. A typical combination is anenzyme cocktail that may comprise, for example, a protease and lipase inconjunction with amylase. When present in the composition, theaforementioned additional enzymes may be present at levels from about0.00001% to about 2%, from about 0.0001% to about 1% or even from about0.001% to about 0.5% enzyme protein by weight of the composition.

Proteases.

Preferably the composition comprises one or more proteases. Suitableproteases include metalloproteases and serine proteases, includingneutral or alkaline microbial serine proteases, such as subtilisins (EC3.4.21.62). Suitable proteases include those of animal, vegetable ormicrobial origin. In one aspect, such suitable protease may be ofmicrobial origin. The suitable proteases include chemically orgenetically modified mutants of the aforementioned suitable proteases.In one aspect, the suitable protease may be a serine protease, such asan alkaline microbial protease or/and a trypsin-type protease. Examplesof suitable neutral or alkaline proteases include:

(a) subtilisins (EC 3.4.21.62), including those derived from Bacillus,such as Bacillus lentus, B. alkalophilus, B. subtilis, B.amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described inU.S. Pat. No. 6,312,936 B1, U.S. Pat. Nos. 5,679,630, 4,760,025,7,262,042 and WO 09/021867.

(b) trypsin-type or chymotrypsin-type proteases, such as trypsin (e.g.,of porcine or bovine origin), including the Fusarium protease describedin WO 89/06270 and the chymotrypsin proteases derived from Cellumonasdescribed in WO 05/052161 and WO 05/052146.

(c) metalloproteases, including those derived from Bacillusamyloliquefaciens described in WO 07/044993A2.

Preferred proteases include those derived from Bacillus gibsonii orBacillus Lentus.

Suitable commercially available protease enzymes include those soldunder the trade names Alcalase®, Savinase®, Primase®, Durazym®,Polarzyme®, Kannase®, Liquanase®, Liquanase Ultra®, Savinase Ultra®,Ovozyme®, Neutrase®, Everlase® and Esperase® by Novozymes A/S (Denmark),those sold under the tradename Maxatase®, Maxacal®, Maxapem®,Properase®, Purafect®, Purafect Prime®, Purafect Ox®, FN3®, FN4®,Excellase® and Purafect OXP® by Genencor International, those sold underthe tradename Opticlean® and Optimase® by Solvay Enzymes, thoseavailable from Henkel/Kemira, namely BLAP (sequence shown in FIG. 29 ofU.S. Pat. No. 5,352,604 with the following mutations S99D+S101R+S103A+V104I+G159S, hereinafter referred to as BLAP), BLAP R (BLAP withS3T+V4I+V199M+V205I+L217D), BLAP X (BLAP with S3T+V4I+V205I) and BLAPF49 (BLAP with S3T+V4I+A194P+V199M+V205I+L217D)—all from Henkel/Kemira;and KAP (Bacillus alkalophilus subtilisin with mutationsA230V+S256G+S259N) from Kao.

Amylases.

Preferably the composition may comprise an amylase. Suitablealpha-amylases include those of bacterial or fungal origin. Chemicallyor genetically modified mutants (variants) are included. A preferredalkaline alpha-amylase is derived from a strain of Bacillus, such asBacillus licheniformis, Bacillus amyloliquefaciens, Bacillusstearothermophilus, Bacillus subtilis, or other Bacillus sp., such asBacillus sp. NCIB 12289, NCIB 12512, NCIB 12513, DSM 9375 (U.S. Pat. No.7,153,818) DSM 12368, DSMZ no. 12649, KSM AP1378 (WO 97/00324), KSM K36or KSM K38 (EP 1 022 334). Preferred amylases include:

(a) the variants described in WO 94/02597, WO 94/18314, WO 96/23874 andWO 97/43424, especially the variants with substitutions in one or moreof the following positions versus the enzyme listed as SEQ ID No. 2 inWO 96/23874: 15, 23, 105, 106, 124, 128, 133, 154, 156, 181, 188, 190,197, 202, 208, 209, 243, 264, 304, 305, 391, 408, and 444.

(b) the variants described in U.S. Pat. No. 5,856,164 and WO 99/23211,WO 96/23873, WO 00/60060 and WO 06/002643, especially the variants withone or more substitutions in the following positions versus the AA560enzyme listed as SEQ ID No. 12 in WO 06/002643:

26, 30, 33, 82, 37, 106, 118, 128, 133, 149, 150, 160, 178, 182, 186,193, 203, 214, 231, 256, 257, 258, 269, 270, 272, 283, 295, 296, 298,299, 303, 304, 305, 311, 314, 315, 318, 319, 339, 345, 361, 378, 383,419, 421, 437, 441, 444, 445, 446, 447, 450, 461, 471, 482, 484,preferably that also contain the deletions of D183* and G184*.

(c) variants exhibiting at least 90% identity with SEQ ID No. 4 inWO06/002643, the wild-type enzyme from Bacillus SP722, especiallyvariants with deletions in the 183 and 184 positions and variantsdescribed in WO 00/60060, which is incorporated herein by reference.

(d) variants exhibiting at least 95% identity with the wild-type enzymefrom Bacillus sp.707 (SEQ ID NO:7 in U.S. Pat. No. 6,093,562),especially those comprising one or more of the following mutations M202,M208, S255, R₁₇₂, and/or M261. Preferably said amylase comprises one ormore of M202L, M202V, M2025, M202T, M2021, M202Q, M202W, S255N and/orR172Q. Particularly preferred are those comprising the M202L or M202Tmutations.

(e) variants described in WO 09/149130, preferably those exhibiting atleast 90% identity with SEQ ID NO: 1 or SEQ ID NO:2 in WO 09/149130, thewild-type enzyme from Geobacillus Stearophermophilus or a truncatedversion thereof.

Suitable commercially available alpha-amylases include DURAMYL®,LIQUEZYME®, TERMAMYL®, TERMAMYL ULTRA®, NATALASE®, SUPRAMYL®,STAINZYME®, STAINZYME PLUS®, FUNGAMYL® and BAN® (Novozymes A/S,Bagsvaerd, Denmark), KEMZYM® AT 9000 Biozym Biotech Trading GmbHWehlistrasse 27b A-1200 Wien Austria, RAPIDASE®, PURASTAR®, ENZYSIZE®,OPTISIZE HT PLUS®, POWERASE® and PURASTAR OXAM® (Genencor InternationalInc., Palo Alto, Calif.) and KAM® (Kao, 14-10 Nihonbashi Kayabacho,1-chome, Chuo-ku Tokyo 103-8210, Japan). In one aspect, suitableamylases include NATALASE®, STAINZYME® and STAINZYME PLUS® and mixturesthereof.

Lipases.

Preferably the invention comprises one or more lipases, including “firstcycle lipases” such as those described in U.S. Pat. No. 6,939,702 B1 andU.S. Patent Application Publication No. 2009/0217464. Preferred lipasesare first-wash lipases. In one embodiment of the invention thecomposition comprises a first wash lipase. First wash lipases includes alipase which is a polypeptide having an amino acid sequence which: (a)has at least 90% identity with the wild-type lipase derived fromHumicola lanuginosa strain DSM 4109; (b) compared to said wild-typelipase, comprises a substitution of an electrically neutral ornegatively charged amino acid at the surface of the three-dimensionalstructure within 15A of E1 or Q249 with a positively charged amino acid;and (c) comprises a peptide addition at the C-terminal; and/or (d)comprises a peptide addition at the N-terminal and/or (e) meets thefollowing limitations: i) comprises a negative amino acid in positionE210 of said wild-type lipase; ii) comprises a negatively charged aminoacid in the region corresponding to positions 90-101 of said wild-typelipase; and iii) comprises a neutral or negative amino acid at aposition corresponding to N94 or said wild-type lipase and/or has anegative or neutral net electric charge in the region corresponding topositions 90-101 of said wild-type lipase. Preferred are variants of thewild-type lipase from Thermomyces lanuginosus comprising one or more ofthe T231R and N233R mutations. The wild-type sequence is the 269 aminoacids (amino acids 23-291) of the Swissprot accession number Swiss-Prot059952 (derived from Thermomyces lanuginosus (Humicola lanuginosa)).Preferred lipases would include those sold under the tradenames Lipex®and Lipolex® and Lipoclean®.

Endoglucanases.

Other preferred enzymes include microbial-derived endoglucanasesexhibiting endo-beta-1,4-glucanase activity (E.C. 3.2.1.4), including abacterial polypeptide endogenous to a member of the genus Bacillus whichhas a sequence of at least 90%, 94%, 97% and even 99% identity to theamino acid sequence SEQ ID NO:2 in U.S. Pat. No. 7,141,403B2) andmixtures thereof. Suitable endoglucanases are sold under the tradenamesCelluclean® and Whitezyme® (Novozymes A/S, Bagsvaerd, Denmark).

Pectate Lyases.

Other preferred enzymes include pectate lyases sold under the tradenamesPectawash®, Pectaway®, Xpect® and mannanases sold under the tradenamesMannaway® (all from Novozymes A/S, Bagsvaerd, Denmark), and Purabrite®(Genencor International Inc., Palo Alto, Calif.).

Bleaching Agents.

It may be preferred for the composition to comprise one or morebleaching agents. Suitable bleaching agents other than bleachingcatalysts include photobleaches, bleach activators, hydrogen peroxide,sources of hydrogen peroxide, pre-formed peracids and mixtures thereof.In general, when a bleaching agent is used, the compositions of thepresent invention may comprise from about 0.1% to about 50% or even fromabout 0.1% to about 25% bleaching agent or mixtures of bleaching agentsby weight of the subject composition. Examples of suitable bleachingagents include:

(1) photobleaches for example sulfonated zinc phthalocyanine sulfonatedaluminium phthalocyanines, xanthene dyes and mixtures thereof;

(2) pre-formed peracids: Suitable preformed peracids include, but arenot limited to compounds selected from the group consisting ofpre-formed peroxyacids or salts thereof typically a percarboxylic acidsand salts, percarbonic acids and salts, perimidic acids and salts,peroxymonosulfuric acids and salts, for example, Oxone®, and mixturesthereof. Suitable examples include peroxycarboxylic acids or saltsthereof, or peroxysulphonic acids or salts thereof. Typicalperoxycarboxylic acid salts suitable for use herein have a chemicalstructure corresponding to the following chemical formula:

wherein: R²⁰ is selected from alkyl, aralkyl, cycloalkyl, aryl orheterocyclic groups; the R²⁰ group can be linear or branched,substituted or unsubstituted; having, when the peracid is hydrophobic,from 6 to 14 carbon atoms, or from 8 to 12 carbon atoms and, when theperacid is hydrophilic, less than 6 carbon atoms or even less than 4carbon atoms and Y is any suitable counter-ion that achieves electriccharge neutrality, preferably Y is selected from hydrogen, sodium orpotassium. Preferably, R¹⁴ is a linear or branched, substituted orunsubstituted C₆₋₉ alkyl. Preferably, the peroxyacid or salt thereof isselected from peroxyhexanoic acid, peroxyheptanoic acid, peroxyoctanoicacid, peroxynonanoic acid, peroxydecanoic acid, any salt thereof, or anycombination thereof. Particularly preferred peroxyacids arephthalimido-peroxy-alkanoic acids, in particular ε-phthalimido peroxyhexanoic acid (PAP). Preferably, the peroxyacid or salt thereof has amelting point in the range of from 30° C. to 60° C. The pre-formedperoxyacid or salt thereof can also be a peroxysulphonic acid or saltthereof, typically having a chemical structure corresponding to thefollowing chemical formula:

wherein: R²¹ is selected from alkyl, aralkyl, cycloalkyl, aryl orheterocyclic groups; the R²¹ group can be linear or branched,substituted or unsubstituted; and Z is any suitable counter-ion thatachieves electric charge neutrality, preferably Z is selected fromhydrogen, sodium or potassium. Preferably R²¹ is a linear or branched,substituted or unsubstituted C₄₋₁₄, preferably C₆₋₁₄ alkyl. Preferablysuch bleach components may be present in the compositions of theinvention in an amount from 0.01 to 50%, most preferably from 0.1% to20%.

(3) sources of hydrogen peroxide, for example, inorganic perhydratesalts, including alkali metal salts such as sodium salts of perborate(usually mono- or tetra-hydrate), percarbonate, persulphate,perphosphate, persilicate salts and mixtures thereof. In one aspect ofthe invention the inorganic perhydrate salts are selected from the groupconsisting of sodium salts of perborate, percarbonate and mixturesthereof. When employed, inorganic perhydrate salts are typically presentin amounts of from 0.05 to 40 wt. %, or 1 to 30 wt. % of the overallfabric and home care product and are typically incorporated into suchfabric and home care products as a crystalline solid that may be coated.Suitable coatings include, inorganic salts such as alkali metalsilicate, carbonate or borate salts or mixtures thereof, or organicmaterials such as water-soluble or dispersible polymers, waxes, oils orfatty soaps; and

(4) bleach activators having R₂₂—(C═O)-L¹ wherein R²² is an alkyl group,optionally branched, having, when the bleach activator is hydrophobic,from 6 to 14 carbon atoms, or from 8 to 12 carbon atoms and, when thebleach activator is hydrophilic, less than 6 carbon atoms or even lessthan 4 carbon atoms; and L¹ is a leaving group. Examples of suitableleaving groups are benzoic acid and derivatives thereof—especiallybenzene sulphonate. Suitable bleach activators include dodecanoyloxybenzene sulphonate, decanoyl oxybenzene sulphonate, decanoyloxybenzoic acid or salts thereof, 3,5,5-trimethyl hexanoyloxybenzenesulphonate, tetraacetyl ethylene diamine (TAED) and nonanoyloxybenzenesulphonate (NOBS). Suitable bleach activators are also disclosed in WO98/17767. While any suitable bleach activator may be employed, in oneaspect of the invention the subject composition may comprise NOBS, TAEDor mixtures thereof.

(5) Bleach Catalysts. The compositions of the present invention may alsoinclude one or more bleach catalysts capable of accepting an oxygen atomfrom a peroxyacid and/or salt thereof, and transferring the oxygen atomto an oxidizeable substrate. Suitable bleach catalysts include, but arenot limited to: iminium cations and polyions; iminium zwitterions;modified amines; modified amine oxides; N-sulphonyl imines; N-phosphonylimines; N-acyl imines; thiadiazole dioxides; perfluoroimines; cyclicsugar ketones and alpha amino-ketones and mixtures thereof. Suitablealpha amino ketones are for example as described in WO 2012/000846 A1,WO 2008/015443 A1, and WO 2008/014965 A1. Suitable mixtures are asdescribed in U.S. Patent Application Publication No. 2007/0173430 A1.Without wishing to be bound by theory, the inventors believe thatcontrolling the electophilicity and hydrophobicity in this abovedescribed manner enables the bleach ingredient to be deliveredsubstantially only to areas of the fabric that are more hydrophobic, andthat contain electron rich soils, including visible chromophores, thatare susceptible to bleaching by highly electrophilic oxidants. In oneaspect, the bleach catalyst has a structure corresponding to generalformula below:

wherein R²³ is selected from the group consisting of 2-ethylhexyl,2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl, n-dodecyl,n-tetradecyl, n-hexadecyl, n-octadecyl, iso-nonyl, iso-decyl,iso-tridecyl and iso-pentadecyl;

(6) The composition may preferably comprise catalytic metal complexes.One preferred type of metal-containing bleach catalyst is a catalystsystem comprising a transition metal cation of defined bleach catalyticactivity, such as copper, iron, titanium, ruthenium, tungsten,molybdenum, or manganese cations, an auxiliary metal cation havinglittle or no bleach catalytic activity, such as zinc or aluminumcations, and a sequestrate having defined stability constants for thecatalytic and auxiliary metal cations, particularlyethylenediaminetetraacetic acid,ethylenediaminetetra(methylenephosphonic acid) and water-soluble saltsthereof. Such catalysts are disclosed in U.S. Pat. No. 4,430,243.

If desired, the compositions herein can be catalyzed by means of amanganese compound. Such compounds and levels of use are well known inthe art and include, for example, the manganese-based catalystsdisclosed in U.S. Pat. No. 5,576,282.

Cobalt bleach catalysts useful herein are known, and are described, forexample, in U.S. Pat. Nos. 5,597,936; 5,595,967. Such cobalt catalystsare readily prepared by known procedures, such as taught for example inU.S. Pat. Nos. 5,597,936, 5,595,967.

Compositions herein may also suitably include a transition metal complexof ligands such as bispidones (WO 05/042532 A1) and/or macropolycyclicrigid ligands—abbreviated as “MRLs”. As a practical matter, and not byway of limitation, the compositions and processes herein can be adjustedto provide on the order of at least one part per hundred million of theactive MRL species in the aqueous washing medium, and will typicallyprovide from about 0.005 ppm to about 25 ppm, from about 0.05 ppm toabout 10 ppm, or even from about 0.1 ppm to about 5 ppm, of the MRL inthe wash liquor.

Suitable transition-metals in the instant transition-metal bleachcatalyst include, for example, manganese, iron and chromium. SuitableMRLs include 5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane.

Suitable transition metal MRLs are readily prepared by known procedures,such as taught for example in WO 00/32601, and U.S. Pat. No. 6,225,464.

When present, the source of hydrogen peroxide/peracid and/or bleachactivator is generally present in the composition in an amount of fromabout 0.1 to about 60 wt. %, from about 0.5 to about 40 wt. % or evenfrom about 0.6 to about 10 wt. % based on the fabric and home careproduct. One or more hydrophobic peracids or precursors thereof may beused in combination with one or more hydrophilic peracid or precursorthereof.

Typically hydrogen peroxide source and bleach activator will beincorporated together. The amounts of hydrogen peroxide source andperacid or bleach activator may be selected such that the molar ratio ofavailable oxygen (from the peroxide source) to peracid is from 1:1 to35:1, or even 2:1 to 10:1.

Surfactant.

Preferably the composition comprises a surfactant or surfactant system.The surfactant can be selected from nonionic, anionic, cationic,amphoteric, ampholytic, amphiphilic, zwitterionic, semi-polar nonionicsurfactants and mixtures thereof. Preferred compositions comprise amixture of surfactants/surfactant system. Preferred surfactant systemscomprise one or more anionic surfactants, most preferably in combinationwith a co-surfactant, most preferably a nonionic and/or amphotericand/or zwitterionic surfactant. Preferred surfactant systems compriseboth anionic and nonionic surfactant, preferably in weight ratios from90:1 to 1:90. In some instances a weight ratio of anionic to nonionicsurfactant of at least 1:1 is preferred. However a ratio below 10:1 maybe preferred. When present, the total surfactant level is preferablyfrom 0.1% to 60%, from 1% to 50% or even from 5% to 40% by weight of thesubject composition.

Preferably the composition comprises an anionic detersive surfactant,preferably sulphate and/or sulphonate surfactants. Preferred examplesinclude alkyl benzene sulphonates, alkyl sulphates and alkyl alkoxylatedsulphates. Preferred sulphonates are C₁₀₋₁₃ alkyl benzene sulphonate.Suitable alkyl benzene sulphonate (LAS) may be obtained, by sulphonatingcommercially available linear alkyl benzene (LAB); suitable LAB includeslow 2-phenyl LAB, such as those supplied by Sasol under the tradenameIsochem® or those supplied by Petresa under the tradename Petrelab®,other suitable LAB include high 2-phenyl LAB, such as those supplied bySasol under the tradename Hyblene®. A suitable anionic detersivesurfactant is alkyl benzene sulphonate that is obtained by DETALcatalyzed process, although other synthesis routes, such as HF, may alsobe suitable. In one aspect a magnesium salt of LAS is used.

Preferred sulphate detersive surfactants include alkyl sulphate,typically C₈-C₁₈ alkyl sulphate, or predominantly C₁₂ alkyl sulphate. Afurther preferred alkyl sulphate is alkyl alkoxylated sulphate,preferably a C₈-C₁₈ alkyl alkoxylated sulphate. Preferably thealkoxylating group is an ethoxylating group. Typically the alkylalkoxylated sulphate has an average degree of alkoxylation of from 0.5to 30 or 20, or from 0.5 to 10. Particularly preferred are C₈-C₁₈ alkylethoxylated sulphate having an average degree of ethoxylation of from0.5 to 10, from 0.5 to 7, from 0.5 to 5 or even from 0.5 to 3.

The alkyl sulphate, alkyl alkoxylated sulphate and alkyl benzenesulphonates may be linear or branched, substituted or un-substituted.When the surfactant is branched, preferably the surfactant will comprisea mid-chain branched sulphate or sulphonate surfactant. Preferably thebranching groups comprise C₁-C₄ alkyl groups, typically methyl and/orethyl groups.

Preferably the composition comprises a nonionic detersive surfactant.Suitable non-ionic surfactants are selected from the group consistingof: C₈-C₁₈ alkyl ethoxylates, such as, NEODOL® non-ionic surfactantsfrom Shell; C₆-C₁₂ alkyl phenol alkoxylates wherein the alkoxylate unitsmay be ethyleneoxy units, propyleneoxy units or a mixture thereof;C₁₂-C₁₈ alcohol and C₆-C₁₂ alkyl phenol condensates with ethyleneoxide/propylene oxide block polymers such as Pluronic® from BASF;C₁₄-C₂₂ mid-chain branched alcohols; C₁₄-C₂₂ mid-chain branched alkylalkoxylates, typically having an average degree of alkoxylation of from1 to 30; alkylpolysaccharides, in one aspect, alkylpolyglycosides;polyhydroxy fatty acid amides; ether capped poly(oxyalkylated) alcoholsurfactants; and mixtures thereof.

Suitable non-ionic detersive surfactants include alkyl polyglucosideand/or an alkyl alkoxylated alcohol.

In one aspect, non-ionic detersive surfactants include alkyl alkoxylatedalcohols, in one aspect C₈₋₁₈ alkyl alkoxylated alcohol, for example aC₈-C₁₈ alkyl ethoxylated alcohol, the alkyl alkoxylated alcohol may havean average degree of alkoxylation of from 1 to 80, preferably from 1 to50, most preferably from 1 to 30, from 1 to 20, or from 1 to 10. In oneaspect, the alkyl alkoxylated alcohol may be a C₈-C₁₈ alkyl ethoxylatedalcohol having an average degree of ethoxylation of from 1 to 10, from 1to 7, more from 1 to 5 or from 3 to 7, or even below 3 or 2. The alkylalkoxylated alcohol can be linear or branched, and substituted orun-substituted.

Suitable nonionic surfactants include those with the tradename Lutensol®from BASF.

Suitable cationic detersive surfactants include alkyl pyridiniumcompounds, alkyl quaternary ammonium compounds, alkyl quaternaryphosphonium compounds, alkyl ternary sulphonium compounds, and mixturesthereof.

Suitable cationic detersive surfactants are quaternary ammoniumcompounds having the general formula:(R²⁵)(R²⁶)(R²⁷)(R²⁸)N⁺X⁻wherein, R²⁵ is a linear or branched, substituted or unsubstitutedC₆-C₁₈ alkyl or alkenyl moiety, R²⁶ and R²⁷ are independently selectedfrom methyl or ethyl moieties, R²⁸ is a hydroxyl, hydroxymethyl or ahydroxyethyl moiety, X is an anion which provides charge neutrality,suitable anions include: halides, for example chloride; sulphate; andsulphonate. Suitable cationic detersive surfactants are mono-C₆₋₁₈ alkylmono-hydroxyethyl di-methyl quaternary ammonium chlorides. Highlysuitable cationic detersive surfactants are mono-C₈₋₁₀ alkylmono-hydroxyethyl di-methyl quaternary ammonium chloride, mono-C₁₀₋₁₂alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride andmono-C₁₀ alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride.

Suitable amphoteric/zwitterionic surfactants include amine oxides andbetaines.

Amine-neutralized anionic surfactants—Anionic surfactants of the presentinvention and adjunct anionic cosurfactants, may exist in an acid form,and said acid form may be neutralized to form a surfactant salt which isdesirable for use in the present detergent compositions. Typical agentsfor neutralization include the metal counterion base such as hydroxides,e.g., NaOH or KOH. Further preferred agents for neutralizing anionicsurfactants of the present invention and adjunct anionic surfactants orcosurfactants in their acid forms include ammonia, amines, oralkanolamines. Alkanolamines are preferred. Suitable non-limitingexamples including monoethanolamine, diethanolamine, triethanolamine,and other linear or branched alkanolamines known in the art; forexample, highly preferred alkanolamines include 2-amino-1-propanol,1-aminopropanol, monoisopropanolamine, or 1-amino-3-propanol. Amineneutralization may be done to a full or partial extent, e.g. part of theanionic surfactant mix may be neutralized with sodium or potassium andpart of the anionic surfactant mix may be neutralized with amines oralkanolamines.

Builders.

Preferably the composition comprises one or more builders or a buildersystem. When a builder is used, the composition of the invention willtypically comprise at least 1%, from 2% to 60% builder. It may bepreferred that the composition comprises low levels of phosphate saltand/or zeolite, for example from 1 to 10 or 5 wt. %. The composition mayeven be substantially free of strong builder; substantially free ofstrong builder means “no deliberately added” zeolite and/or phosphate.Typical zeolite builders include zeolite A, zeolite P and zeolite MAP. Atypical phosphate builder is sodium tri-polyphosphate.

Chelating Agent.

Preferably the composition comprises chelating agents and/or crystalgrowth inhibitor. Suitable molecules include copper, iron and/ormanganese chelating agents and mixtures thereof. Suitable moleculesinclude aminocarboxylates, aminophosphonates, succinates, salts thereof,and mixtures thereof. Non-limiting examples of suitable chelants for useherein include ethylenediaminetetracetates,N-(hydroxyethyl)ethylenediaminetriacetates, nitrilotriacetates,ethylenediamine tetraproprionates, triethylenetetraaminehexacetates,diethylenetriamine-pentaacetates, ethanoldiglycines,ethylenediaminetetrakis(methylenephosphonates), diethylenetriaminepenta(methylene phosphonic acid) (DTPMP), ethylenediamine disuccinate(EDDS), hydroxyethanedimethylenephosphonic acid (HEDP),methylglycinediacetic acid (MGDA), diethylenetriaminepentaacetic acid(DTPA), salts thereof, and mixtures thereof. Other nonlimiting examplesof chelants of use in the present invention are found in U.S. Pat. Nos.7,445,644 and 7,585,376 and U.S. Patent Application Publication No.2009/0176684A1. Other suitable chelating agents for use herein are thecommercial DEQUEST series, and chelants from Monsanto, DuPont, andNalco, Inc.

Dye Transfer Inhibitor (DTI).

The composition may comprise one or more dye transfer inhibiting agents.In one embodiment of the invention the inventors have surprisingly foundthat compositions comprising polymeric dye transfer inhibiting agents inaddition to the specified dye give improved performance. This issurprising because these polymers prevent dye deposition. Suitable dyetransfer inhibitors include, but are not limited to,polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers ofN-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones andpolyvinylimidazoles or mixtures thereof. Suitable examples includePVP-K15, PVP-K30, ChromaBond S-400, ChromaBond S-403E and ChromabondS-100 from Ashland Aqualon, and Sokalan HP165, Sokalan HP50, SokalanHP53, Sokalan HP59, Sokalan® HP 56K, Sokalan® HP 66 from BASF. Othersuitable DTIs are as described in WO2012/004134. When present in asubject composition, the dye transfer inhibiting agents may be presentat levels from about 0.0001% to about 10%, from about 0.01% to about 5%or even from about 0.1% to about 3% by weight of the composition.

Fluorescent Brightener.

Preferably the composition comprises one or more fluorescent brightener.Commercial optical brighteners which may be useful in the presentinvention can be classified into subgroups, which include, but are notlimited to, derivatives of stilbene, pyrazoline, coumarin, carboxylicacid, methinecyanines, dibenzothiophene-5,5-dioxide, azoles, 5- and6-membered-ring heterocycles, and other miscellaneous agents.Particularly preferred brighteners are selected from: sodium 2(4-styryl-3-sulfophenyl)-2H-napthol[1,2-d]triazole, disodium4,4′-bis{[(4-anilino-6-(N methyl-N-2 hydroxyethyl)amino1,3,5-triazin-2-yl)]amino}stilbene-2-2-disulfonate, disodium4,4′-bis{[(4-anilino-6-morpholino-I,3,5-triazin-2-yl)]amino}stilbene-2-2′disulfonate, and disodium4,4′-bis(2-sulfostyryl)biphenyl. Other examples of such brighteners aredisclosed in “The Production and Application of Fluorescent BrighteningAgents”, M. Zahradnik, Published by John Wiley & Sons, New York (1982).Specific nonlimiting examples of optical brighteners which are useful inthe present compositions are those identified in U.S. Pat. Nos.4,790,856 and 3,646,015. Suitable optical brighteners also includecompounds selected from the above-identified groups which have beensubstituted with one or more oligomeric or polymeric chains, such as oneor more oxyalkylene chains. Suitable examples of such opticalbrighteners are disclosed in U.S. Pat. Nos. 8,262,743, 9,018,151,8,262,744, 8,454,711, and 8,740,997.

A preferred brightener has the structure below:

Suitable fluorescent brightener levels include lower levels of fromabout 0.01, from about 0.05, from about 0.1 or even from about 0.2 wt %to upper levels of 0.5 or even 0.75 wt %.

In one aspect the brightener may be loaded onto a clay to form aparticle.

Preferred brighteners are totally or predominantly (typically at least50 wt. %, at least 75 wt. %, at least 90 wt. %, at least 99 wt. %), inalpha-crystalline form. A highly preferred brightener comprises C.I.fluorescent brightener 260, preferably having the following structure:

This can be particularly useful as it dissolves well in cold water, forexample below 30 or 25 or even 20° C.

Preferably brighteners are incorporated in the composition in micronizedparticulate form, most preferably having a weight average primaryparticle size of from 3 to 30 micrometers, from 3 micrometers to 20micrometers, or from 3 to 10 micrometers.

The composition may comprise C.I. fluorescent brightener 260 inbeta-crystalline form, and the weight ratio of: (i) C.I. fluorescentbrightener 260 in alpha-crystalline form, to (ii) C.I. fluorescentbrightener 260 in beta-crystalline form may be at least 0.1, or at least0.6.

BE 680847 relates to a process for making C.I fluorescent brightener 260in alpha-crystalline form.

Silicate Salts.

The composition may preferably also contain silicate salts, such assodium or potassium silicate. The composition may comprise from 0 wt. %to less than 10 wt. % silicate salt, to 9 wt. %, or to 8 wt. %, or to 7wt. %, or to 6 wt. %, or to 5 wt. %, or to 4 wt. %, or to 3 wt. %, oreven to 2 wt. %, and preferably from above 0 wt. %, or from 0.5 wt. %,or even from 1 wt. % silicate salt. A suitable silicate salt is sodiumsilicate.

Dispersants.

The composition may preferably also contain dispersants. Suitablewater-soluble organic materials include the homo- or co-polymeric acidsor their salts, in which the polycarboxylic acid comprises at least twocarboxyl radicals separated from each other by not more than two carbonatoms.

Enzyme Stabilisers.

The composition may preferably comprise enzyme stabilizers. Anyconventional enzyme stabilizer may be used, for example by the presenceof water-soluble sources of calcium and/or magnesium ions in thefinished fabric and home care products that provide such ions to theenzymes. In case of aqueous compositions comprising protease, areversible protease inhibitor, such as a boron compound includingborate, or preferably 4-formyl phenylboronic acid, phenylboronic acidand derivatives thereof, or compounds such as calcium formate, sodiumformate and 1,2-propane diol can be added to further improve stability.

Solvent System.

The solvent system in the present compositions can be a solvent systemcontaining water alone or mixtures of organic solvents either without orpreferably with water. Preferred organic solvents include1,2-propanediol, ethanol, glycerol, dipropylene glycol, methyl propanediol and mixtures thereof. Other lower alcohols, C₁-C₄ alkanolaminessuch as monoethanolamine and triethanolamine, can also be used. Solventsystems can be absent, for example from anhydrous solid embodiments ofthe invention, but more typically are present at levels in the range offrom about 0.1% to about 98%, preferably at least about 1% to about 50%,more usually from about 5% to about 25%.

In some embodiments of the invention, the composition is in the form ofa structured liquid. Such structured liquids can either be internallystructured, whereby the structure is formed by primary ingredients (e.g.surfactant material) and/or externally structured by providing a threedimensional matrix structure using secondary ingredients (e.g. polymers,clay and/or silicate material), for use e.g. as thickeners. Thecomposition may comprise a structurant, preferably from 0.01 wt. % to 5wt. %, from 0.1 wt. % to 2.0 wt. % structurant. Examples of suitablestructurants are given in U.S. Patent Application Publication No.2006/0205631A1, U.S. Patent Application Publication No. 2005/0203213A1,U.S. Pat. Nos. 7,294,611, 6,855,680. The structurant is typicallyselected from the group consisting of diglycerides and triglycerides,ethylene glycol distearate, microcrystalline cellulose, cellulose-basedmaterials, microfiber cellulose, hydrophobically modifiedalkali-swellable emulsions such as Polygel W30 (3VSigma), biopolymers,xanthan gum, gellan gum, hydrogenated castor oil, derivatives ofhydrogenated castor oil such as non-ethoxylated derivatieves thereof andmixtures thereof, in particular, those selected from the group ofhydrogenated castor oil, derivatives of hydrogenated castor oil,microfibullar cellulose, hydroxyfunctional crystalline materials, longchain fatty alcohols, 12-hydroxystearic acids, clays and mixturesthereof. A preferred structurant is described in. U.S. Pat. No.6,855,680 which defines suitable hydroxyfunctional crystalline materialsin detail. Preferred is hydrogenated castor oil. Non-limiting examplesof useful structurants include. Such structurants have a thread-likestructuring system having a range of aspect ratios. Other suitablestructurants and the processes for making them are described in WO2010/034736.

The composition of the present invention may comprise a high meltingpoint fatty compound. The high melting point fatty compound usefulherein has a melting point of 25° C. or higher, and is selected from thegroup consisting of fatty alcohols, fatty acids, fatty alcoholderivatives, fatty acid derivatives, and mixtures thereof. Suchcompounds of low melting point are not intended to be included in thissection. Non-limiting examples of the high melting point compounds arefound in International Cosmetic Ingredient Dictionary, Fifth Edition,1993, and CTFA Cosmetic Ingredient Handbook, Second Edition, 1992. Whenpresent, the high melting point fatty compound is preferably included inthe composition at a level of from 0.1% to 40%, preferably from 1% to30%, more preferably from 1.5% to 16% by weight of the composition, from1.5% to 8% in view of providing improved conditioning benefits such asslippery feel during the application to wet hair, softness andmoisturized feel on dry hair.

Cationic Polymer.

The compositions of the present invention may contain a cationicpolymer. Concentrations of the cationic polymer in the compositiontypically range from 0.05% to 3%, in another embodiment from 0.075% to2.0%, and in yet another embodiment from 0.1% to 1.0%. Suitable cationicpolymers will have cationic charge densities of at least 0.5 meq/gm, inanother embodiment at least 0.9 meq/gm, in another embodiment at least1.2 meq/gm, in yet another embodiment at least 1.5 meq/gm, but in oneembodiment also less than 7 meq/gm, and in another embodiment less than5 meq/gm, at the pH of intended use of the composition, which pH willgenerally range from pH 3 to pH 9, in one embodiment between pH 4 and pH8. Herein, “cationic charge density” of a polymer refers to the ratio ofthe number of positive charges on the polymer to the molecular weight ofthe polymer. The average molecular weight of such suitable cationicpolymers will generally be between 10,000 and 10 million, in oneembodiment between 50,000 and 5 million, and in another embodimentbetween 100,000 and 3 million.

Suitable cationic polymers for use in the compositions of the presentinvention contain cationic nitrogen-containing moieties such asquaternary ammonium or cationic protonated amino moieties. Any anioniccounterions can be used in association with the cationic polymers solong as the polymers remain soluble in water, in the composition, or ina coacervate phase of the composition, and so long as the counterionsare physically and chemically compatible with the essential componentsof the composition or do not otherwise unduly impair productperformance, stability or aesthetics. Nonlimiting examples of suchcounterions include halides (e.g., chloride, fluoride, bromide, iodide),sulfate and methylsulfate.

Nonlimiting examples of such polymers are described in the CTFA CosmeticIngredient Dictionary, 3rd edition, edited by Estrin, Crosley, andHaynes, (The Cosmetic, Toiletry, and Fragrance Association, Inc.,Washington, D.C. (1982)).

Other suitable cationic polymers for use in the composition includepolysaccharide polymers, cationic guar gum derivatives, quaternarynitrogen-containing cellulose ethers, synthetic polymers, copolymers ofetherified cellulose, guar and starch. When used, the cationic polymersherein are either soluble in the composition or are soluble in a complexcoacervate phase in the composition formed by the cationic polymer andthe anionic, amphoteric and/or zwitterionic surfactant componentdescribed hereinbefore. Complex coacervates of the cationic polymer canalso be formed with other charged materials in the composition.

Suitable cationic polymers are described in U.S. Pat. Nos. 3,962,418 and3,958,581; and U.S. Patent Application Publication No. 2007/0207109A1.

Nonionic Polymer.

The composition of the present invention may include a nonionic polymeras a conditioning agent. Polyalkylene glycols having a molecular weightof more than 1,000 are nonionic polymers suitable for use as such acondition agent. Useful are those having the following general formula:

wherein each R³⁰ is selected from the group consisting of hydrogen andmethyl, and x is a positive integer having a value great enough to yieldthe desired molecular weight. Conditioning agents, and in particularsilicones, may be included in the composition. The conditioning agentsuseful in the compositions of the present invention typically comprise awater insoluble, water dispersible, non-volatile, liquid that formsemulsified, liquid particles. Suitable conditioning agents for use inthe composition are those conditioning agents characterized generally assilicones (e.g., silicone oils, cationic silicones, silicone gums, highrefractive silicones, and silicone resins), organic conditioning oils(e.g., hydrocarbon oils, polyolefins, and fatty esters) or combinationsthereof, or those conditioning agents which otherwise form liquid,dispersed particles in the aqueous surfactant matrix herein. Suchconditioning agents should be physically and chemically compatible withthe essential components of the composition, and should not otherwiseunduly impair product stability, aesthetics or performance.

The concentration of the conditioning agent in the composition should besufficient to provide the desired conditioning benefits. Suchconcentration can vary with the conditioning agent, the conditioningperformance desired, the average size of the conditioning agentparticles, the type and concentration of other components, and otherlike factors.

The concentration of the silicone conditioning agent typically rangesfrom about 0.01% to about 10%. Non-limiting examples of suitablesilicone conditioning agents, and optional suspending agents for thesilicone, are described in U.S. Reissue Pat. No. 34,584, U.S. Pat. Nos.5,104,646; 5,106,609; 4,152,416; 2,826,551; 3,964,500; 4,364,837;6,607,717; 6,482,969; 5,807,956; 5,981,681; 6,207,782; 7,465,439;7,041,767; 7,217,777; U.S. Patent Application Publication Nos.2007/0286837A1; 2005/0048549A1; 2007/0041929A1; British Pat. No.849,433; German Patent No. DE 10036533, which are all incorporatedherein by reference; Chemistry and Technology of Silicones, New York:Academic Press (1968); General Electric Silicone Rubber Product DataSheets SE 30, SE 33, SE 54 and SE 76; Silicon Compounds, PetrarchSystems, Inc. (1984); and in Encyclopedia of Polymer Science andEngineering, vol. 15, 2d ed., pp 204-308, John Wiley & Sons, Inc.(1989).

Organic Conditioning Oil.

The compositions of the present invention may also comprise from about0.05% to about 3% of at least one organic conditioning oil as theconditioning agent, either alone or in combination with otherconditioning agents, such as the silicones (described herein). Suitableconditioning oils include hydrocarbon oils, polyolefins, and fattyesters. Also suitable for use in the compositions herein are theconditioning agents described by the Procter & Gamble Company in U.S.Pat. Nos. 5,674,478, and 5,750,122. Also suitable for use herein arethose conditioning agents described in U.S. Pat. Nos. 4,529,586;4,507,280; 4,663,158; 4,197,865; 4,217,914; 4,381,919; and 4,422,853.

Hygiene Agent.

The compositions of the present invention may also comprise componentsto deliver hygiene and/or malodour benefits such as one or more of zincricinoleate, thymol, quaternary ammonium salts such as Bardac®,polyethylenimines (such as Lupasol® from BASF) and zinc complexesthereof, silver and silver compounds, especially those designed toslowly release Ag+ or nano-silver dispersions.

Probiotics.

The composition may comprise probiotics, such as those described in WO2009/043709.

Suds Boosters.

The composition may preferably comprise suds boosters if high sudsing isdesired. Suitable examples are the C₁₀-C₁₆ alkanolamides or C₁₀-C₁₄alkyl sulphates, which are preferably incorporated at 1%-10% levels. TheC₁₀-C₁₄ monoethanol and diethanol amides illustrate a typical class ofsuch suds boosters. Use of such suds boosters with high sudsing adjunctsurfactants such as the amine oxides, betaines and sultaines noted aboveis also advantageous. If desired, water-soluble magnesium and/or calciumsalts such as MgCl₂, MgSO₄, CaCl₂, CaSO₄ and the like, can be added atlevels of, typically, 0.1%-2%, to provide additional suds and to enhancegrease removal performance.

Suds Supressor.

Compounds for reducing or suppressing the formation of suds may beincorporated into the compositions of the present invention. Sudssuppression can be of particular importance in the so-called “highconcentration cleaning process” as described in U.S. Pat. Nos. 4,489,455and 4,489,574, and in front-loading-style washing machines. A widevariety of materials may be used as suds suppressors, and sudssuppressors are well known to those skilled in the art. See, forexample, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition,Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). Examples ofsuds supressors include monocarboxylic fatty acid and soluble saltstherein, high molecular weight hydrocarbons such as paraffin, fatty acidesters (e.g., fatty acid triglycerides), fatty acid esters of monovalentalcohols, aliphatic C₁₈-C₄₀ ketones (e.g., stearone), N-alkylated aminotriazines, waxy hydrocarbons preferably having a melting point belowabout 100° C., silicone suds suppressors, and secondary alcohols. Sudssupressors are described in U.S. Pat. Nos. 2,954,347; 4,265,779;4,265,779; 3,455,839; 3,933,672; 4,652,392; 4,978,471; 4,983,316;5,288,431; 4,639,489; 4,749,740; 4,798,679; and 4,075,118; EuropeanPatent Application No. 89307851.9; EP 150 872; and DOS 2,124,526.

For any detergent compositions to be used in automatic laundry washingmachines, suds should not form to the extent that they overflow thewashing machine. Suds suppressors, when utilized, are preferably presentin a “suds suppressing amount. By “suds suppressing amount” is meantthat the formulator of the composition can select an amount of this sudscontrolling agent that will sufficiently control the suds to result in alow-sudsing laundry detergent for use in automatic laundry washingmachines. The compositions herein will generally comprise from 0% to 10%of suds suppressor. When utilized as suds suppressors, monocarboxylicfatty acids, and salts therein, will be present typically in amounts upto 5%, by weight, of the detergent composition. Preferably, from 0.5% to3% of fatty monocarboxylate suds suppressor is utilized. Silicone sudssuppressors are typically utilized in amounts up to 2.0%, by weight, ofthe detergent composition, although higher amounts may be used.Monostearyl phosphate suds suppressors are generally utilized in amountsranging from 0.1% to 2%, by weight, of the composition. Hydrocarbon sudssuppressors are typically utilized in amounts ranging from 0.01% to5.0%, although higher levels can be used. The alcohol suds suppressorsare typically used at 0.2%-3% by weight of the finished compositions.

Pearlescent Agents.

Pearlescent agents as described in WO2011/163457 may be incorporatedinto the compositions of the invention.

Perfume.

Preferably the composition comprises a perfume, preferably in the rangefrom 0.001 to 3 wt. %, most preferably from 0.1 to 1 wt. %. Manysuitable examples of perfumes are provided in the CTFA (Cosmetic,Toiletry and Fragrance Association) 1992 International Buyers Guide,published by CFTA Publications and OPD 1993 Chemicals Buyers Directory80th Annual Edition, published by Schnell Publishing Co. It is usual fora plurality of perfume components to be present in the compositions ofthe invention, for example four, five, six, seven or more. In perfumemixtures preferably 15 to 25 wt. % are top notes. Top notes are definedby Poucher (Journal of the Society of Cosmetic Chemists 6(2):80 [1995]).Preferred top notes include rose oxide, citrus oils, linalyl acetate,lavender, linalool, dihydromyrcenol and cis-3-hexanol.

Packaging.

Any conventional packaging may be used and the packaging may be fully orpartially transparent so that the consumer can see the color of theproduct which may be provided or contributed to by the color of the dyesessential to the invention. UV absorbing compounds may be included insome or all of the packaging.

Process of Making Compositions.

The compositions of the invention may be in any useful form, asdescribed above. They may be made by any process chosen by theformulator, non-limiting examples of which are described in the examplesand in U.S. Pat. No. 4,990,280; U.S. Patent Application Publication No.2003/0087791 A1; U.S. Patent Application Publication No. 2003/0087790A1;U.S. Patent Application Publication No. 2005/0003983A1; U.S. PatentApplication Publication No. 2004/0048764A1; U.S. Pat. Nos. 4,762,636;6,291,412; U.S. Patent Application Publication No. 20050227891A1; EP1070115A2; U.S. Pat. Nos. 5,879,584; 5,691,297; 5,574,005; U.S. Pat.Nos. 5,569,645; 5,565,422; 5,516,448; and 5,489,392.

When in the form of a liquid, the laundry care compositions of theinvention may be aqueous (typically above 2 wt. % or even above 5 or 10wt. % total water, up to 90 or up to 80 wt. % or 70 wt. % total water)or non-aqueous (typically below 2 wt. % total water content). Typicallythe compositions of the invention will be in the form of an aqueoussolution or uniform dispersion or suspension of surfactant, shading dye,and certain optional other ingredients, some of which may normally be insolid form, that have been combined with the normally liquid componentsof the composition, such as the liquid alcohol ethoxylate nonionic, theaqueous liquid carrier, and any other normally liquid optionalingredients. Such a solution, dispersion or suspension will beacceptably phase stable. When in the form of a liquid, the laundry carecompositions of the invention preferably have viscosity from 1 to 1500centipoises (1-1500 mPa*s), more preferably from 100 to 1000 centipoises(100-1000 mPa*s), and most preferably from 200 to 500 centipoises(200-500 mPa*s) at 20 s-1 and 21° C. Viscosity can be determined byconventional methods. Viscosity may be measured using an AR 550rheometer from TA instruments using a plate steel spindle at 40 mmdiameter and a gap size of 500 The high shear viscosity at 20 s-1 andlow shear viscosity at 0.05-1 can be obtained from a logarithmic shearrate sweep from 0.1-1 to 25-1 in 3 minutes time at 21 C. The preferredrheology described therein may be achieved using internal existingstructuring with detergent ingredients or by employing an externalrheology modifier. More preferably the laundry care compositions, suchas detergent liquid compositions have a high shear rate viscosity offrom about 100 centipoise to 1500 centipoise, more preferably from 100to 1000 cps. Unit Dose laundry care compositions, such as detergentliquid compositions have high shear rate viscosity of from 400 to 1000cps. Laundry care compositions such as laundry softening compositionstypically have high shear rate viscosity of from 10 to 1000, morepreferably from 10 to 800 cps, most preferably from 10 to 500 cps. Handdishwashing compositions have high shear rate viscosity of from 300 to4000 cps, more preferably 300 to 1000 cps.

The liquid compositions, preferably liquid detergent compositions hereincan be prepared by combining the components thereof in any convenientorder and by mixing, e.g., agitating, the resulting componentcombination to form a phase stable liquid detergent composition. In aprocess for preparing such compositions, a liquid matrix is formedcontaining at least a major proportion, or even substantially all, ofthe liquid components, e.g., nonionic surfactant, the non-surface activeliquid carriers and other optional liquid components, with the liquidcomponents being thoroughly admixed by imparting shear agitation to thisliquid combination. For example, rapid stirring with a mechanicalstirrer may usefully be employed. While shear agitation is maintained,substantially all of any anionic surfactants and the solid formingredients can be added. Agitation of the mixture is continued, and ifnecessary, can be increased at this point to form a solution or auniform dispersion of insoluble solid phase particulates within theliquid phase. After some or all of the solid-form materials have beenadded to this agitated mixture, particles of any enzyme material to beincluded, e.g., enzyme prills, are incorporated. As a variation of thecomposition preparation procedure hereinbefore described, one or more ofthe solid components may be added to the agitated mixture as a solutionor slurry of particles premixed with a minor portion of one or more ofthe liquid components. After addition of all of the compositioncomponents, agitation of the mixture is continued for a period of timesufficient to form compositions having the requisite viscosity and phasestability characteristics. Frequently this will involve agitation for aperiod of from about 30 to 60 minutes.

In one aspect of forming the liquid compositions, the dye is firstcombined with one or more liquid components to form a dye premix, andthis dye premix is added to a composition formulation containing asubstantial portion, for example more than 50% by weight, morespecifically, more than 70% by weight, and yet more specifically, morethan 90% by weight, of the balance of components of the laundrydetergent composition. For example, in the methodology described above,both the dye premix and the enzyme component are added at a final stageof component additions. In another aspect, the dye is encapsulated priorto addition to the detergent composition, the encapsulated dye issuspended in a structured liquid, and the suspension is added to acomposition formulation containing a substantial portion of the balanceof components of the laundry detergent composition.

Pouches.

In a preferred embodiment of the invention, the composition is providedin the form of a unitized dose, either tablet form or preferably in theform of a liquid/solid (optionally granules)/gel/paste held within awater-soluble film in what is known as a pouch or pod. The compositioncan be encapsulated in a single or multi-compartment pouch.Multi-compartment pouches are described in more detail in EP 2133410 A.When the composition is present in a multi-compartment pouch, thecomposition of the invention may be in one or two or more compartments,thus the dye may be present in one or more compartments, optionally allcompartments. Non-shading dyes or pigments or other aesthetics may alsobe used in one or more compartments. In one embodiment the compositionis present in a single compartment of a multi-compartment pouch.

Suitable film for forming the pouches is soluble or dispersible inwater, and preferably has a water-solubility/dispersibility of at least50%, preferably at least 75% or even at least 95%, as measured by themethod set out here after using a glass-filter with a maximum pore sizeof 20 microns:

50 grams±0.1 gram of pouch material is added in a pre-weighed 400 mlbeaker and 245 ml±1 ml of distilled water is added. This is stirredvigorously on a magnetic stirrer set at 600 rpm for 30 minutes. Then,the mixture is filtered through a folded qualitative sintered-glassfilter with a pore size as defined above (max. 20 micron). The water isdried off from the collected filtrate by any conventional method, andthe weight of the remaining material is determined (which is thedissolved or dispersed fraction). Then, the percentage solubility ordispersability can be calculated.

Preferred film materials are polymeric materials. The film material canbe obtained, for example, by casting, blow-moulding, extrusion or blownextrusion of the polymeric material, as known in the art. Preferredpolymers, copolymers or derivatives thereof suitable for use as pouchmaterial are selected from polyvinyl alcohols, polyvinyl pyrrolidone,polyalkylene oxides, acrylamide, acrylic acid, cellulose, celluloseethers, cellulose esters, cellulose amides, polyvinyl acetates,polycarboxylic acids and salts, polyaminoacids or peptides, polyamides,polyacrylamide, copolymers of maleic/acrylic acids, polysaccharidesincluding starch and gelatine, natural gums such as xanthum andcarragum. More preferred polymers are selected from polyacrylates andwater-soluble acrylate copolymers, methylcellulose,carboxymethylcellulose sodium, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropyl methylcellulose, maltodextrin,polymethacrylates, and most preferably selected from polyvinyl alcohols,polyvinyl alcohol copolymers and hydroxypropyl methyl cellulose (HPMC),and combinations thereof. Preferably, the level of polymer in the pouchmaterial, for example a PVA polymer, is at least 60%. The polymer canhave any weight average molecular weight, preferably from about 1000 to1,000,000, more preferably from about 10,000 to 300,000 yet morepreferably from about 20,000 to 150,000. Mixtures of polymers can alsobe used as the pouch material. This can be beneficial to control themechanical and/or dissolution properties of the compartments or pouch,depending on the application thereof and the required needs. Suitablemixtures include for example mixtures wherein one polymer has a higherwater-solubility than another polymer, and/or one polymer has a highermechanical strength than another polymer. Also suitable are mixtures ofpolymers having different weight average molecular weights, for examplea mixture of PVA or a copolymer thereof of a weight average molecularweight of about 10,000-40,000, preferably around 20,000, and of PVA orcopolymer thereof, with a weight average molecular weight of about100,000 to 300,000, preferably around 150,000. Also suitable herein arepolymer blend compositions, for example comprising hydrolyticallydegradable and water-soluble polymer blends such as polylactide andpolyvinyl alcohol, obtained by mixing polylactide and polyvinyl alcohol,typically comprising about 1-35% by weight polylactide and about 65% to99% by weight polyvinyl alcohol. Preferred for use herein are polymerswhich are from about 60% to about 98% hydrolysed, preferably about 80%to about 90% hydrolysed, to improve the dissolution characteristics ofthe material.

Naturally, different film material and/or films of different thicknessmay be employed in making the compartments of the present invention. Abenefit in selecting different films is that the resulting compartmentsmay exhibit different solubility or release characteristics.

Most preferred film materials are PVA films known under the MonoSoltrade reference M8630, M8900, H8779 (as described in the Applicantsco-pending applications ref 44528 and 11599) and those described in U.S.Pat. Nos. 6,166,117 and 6,787,512 and PVA films of correspondingsolubility and deformability characteristics.

The film material herein can also comprise one or more additiveingredients. For example, it can be beneficial to add plasticisers, forexample glycerol, ethylene glycol, diethyleneglycol, propylene glycol,sorbitol and mixtures thereof. Other additives include functionaldetergent additives to be delivered to the wash water, for exampleorganic polymeric dispersants, etc.

Process for Making the Water-Soluble Pouch.

The compositions of the invention in pouch form may be made using anysuitable equipment and method. However the multi-compartment pouches arepreferably made using the horizontal form filling process. The film ispreferably wetting, more preferably heated to increase the malleabilitythereof. Even more preferably, the method also involves the use of avacuum to draw the film into a suitable mold. The vacuum drawing thefilm into the mold can be applied for 0.2 to 5 seconds, preferably 0.3to 3 or even more preferably 0.5 to 1.5 seconds, once the film is on thehorizontal portion of the surface. This vacuum may preferably be suchthat it provides an under-pressure of between −100 mbar to −1000 mbar,or even from −200 mbar to −600 mbar.

The molds, in which the pouches are made, can have any shape, length,width and depth, depending on the required dimensions of the pouches.The molds can also vary in size and shape from one to another, ifdesirable. For example, it may be preferred that the volume of the finalpouches is between 5 and 300 ml, or even 10 and 150 ml or even 20 and100 ml and that the mold sizes are adjusted accordingly.

Heat can be applied to the film, in the process commonly known asthermoforming, by any means. For example the film may be heated directlyby passing it under a heating element or through hot air, prior tofeeding it onto the surface or once on the surface. Alternatively it maybe heated indirectly, for example by heating the surface or applying ahot item onto the film. Most preferably the film is heated using aninfrared light. The film is preferably heated to a temperature of 50 to120° C., or even 60 to 90° C. Alternatively, the film can be wetted byany mean, for example directly by spraying a wetting agent (includingwater, solutions of the film material or plasticizers for the filmmaterial) onto the film, prior to feeding it onto the surface or once onthe surface, or indirectly by wetting the surface or by applying a wetitem onto the film.

In the case of pouches comprising powders it is advantageous to pinprick the film for a number of reasons: (a) to reduce the possibility offilm defects during the pouch formation, for example film defects givingrise to rupture of the film can be generated if the stretching of thefilm is too fast; (b) to permit the release of any gases derived fromthe product enclosed in the pouch, as for example oxygen formation inthe case of powders containing bleach; and/or (c) to allow thecontinuous release of perfume. Moreover, when heat and/or wetting isused, pin pricking can be used before, during or after the use of thevacuum, preferably during or before application of the vacuum. Preferredis thus that each mold comprises one or more holes which are connectedto a system which can provide a vacuum through these holes, onto thefilm above the holes, as described herein in more detail.

Once a film has been heated/wetted, it is drawn into an appropriatemold, preferably using a vacuum. The filling of the moulded film can bedone by any known method for filling (moving) items. The most preferredmethod will depend on the product form and speed of filling required.Preferably the moulded film is filled by in-line filling techniques. Thefilled, open pouches are then closed, using a second film, by anysuitable method. Preferably, this is also done while in horizontalposition and in continuous, constant motion. Preferably the closing isdone by continuously feeding a second material or film, preferablywater-soluble film, over and onto the web of open pouches and thenpreferably sealing the first film and second film together, typically inthe area between the molds and thus between the pouches.

Preferred methods of sealing include heat sealing, solvent welding, andsolvent or wet sealing. It is preferred that only the area which is toform the seal, is treated with heat or solvent. The heat or solvent canbe applied by any method, preferably on the closing material, preferablyonly on the areas which are to form the seal. If solvent or wet sealingor welding is used, it may be preferred that heat is also applied.Preferred wet or solvent sealing/welding methods include applyingselectively solvent onto the area between the molds, or on the closingmaterial, by for example, spraying or printing this onto these areas,and then applying pressure onto these areas, to form the seal. Sealingrolls and belts as described above (optionally also providing heat) canbe used, for example.

The formed pouches can then be cut by a cutting device. Cutting can bedone using any known method. It may be preferred that the cutting isalso done in continuous manner, and preferably with constant speed andpreferably while in horizontal position. The cutting device can, forexample, be a sharp item or a hot item, whereby in the latter case, thehot item ‘burns’ through the film/sealing area.

The different compartments of a multi-compartment pouch may be madetogether in a side-by-side style and consecutive pouches are not cut.Alternatively, the compartments can be made separately. According tothis process and preferred arrangement, the pouches are made accordingto the process comprising the steps of:

-   -   (a) forming an first compartment (as described above);    -   (b) forming a recess within some or all of the closed        compartment formed in step (a), to generate a second moulded        compartment superposed above the first compartment;    -   (c) filling and closing the second compartments by means of a        third film;    -   (d) sealing said first, second and third films; and    -   (e) cutting the films to produce a multi-compartment pouch.

Said recess formed in step b is preferably achieved by applying a vacuumto the compartment prepared in step a).

Alternatively the second, and optionally third, compartment(s) can bemade in a separate step and then combined with the first compartment asdescribed in European Patent Application No. EP 08101442.5 which isincorporated herein by reference. A particularly preferred processcomprises the steps of:

-   -   (a) forming a first compartment, optionally using heat and/or        vacuum, using a first film on a first forming machine;    -   (b) filling said first compartment with a first composition;    -   (c) on a second forming machine, deforming a second film,        optionally using heat and vacuum, to make a second and        optionally third moulded compartment;    -   (d) filling the second and optionally third compartments;    -   (e) sealing the second and optionally third compartment using a        third film;    -   (f) placing the sealed second and optionally third compartments        onto the first compartment;    -   (g) sealing the first, second and optionally third compartments;        and    -   (h) cutting the films to produce a multi-compartment pouch.

The first and second forming machines are selected based on theirsuitability to perform the above process. The first forming machine ispreferably a horizontal forming machine. The second forming machine ispreferably a rotary drum forming machine, preferably located above thefirst forming machine.

It will be understood moreover that by the use of appropriate feedstations, it is possible to manufacture multi-compartment pouchesincorporating a number of different or distinctive compositions and/ordifferent or distinctive liquid, gel or paste compositions.

Solid Form.

As noted previously, the laundry care compositions may be in a solidform. Suitable solid forms include tablets and particulate forms, forexample, granular particles, flakes or sheets. Various techniques forforming detergent compositions in such solid forms are well known in theart and may be used herein. In one aspect, for example when thecomposition is in the form of a granular particle, the dye is providedin particulate form, optionally including additional but not allcomponents of the laundry detergent composition. The dye particulate iscombined with one or more additional particulates containing a balanceof components of the laundry detergent composition. Further, the dye,optionally including additional but not all components of the laundrydetergent composition, may be provided in an encapsulated form, and theshading dye encapsulate is combined with particulates containing asubstantial balance of components of the laundry detergent composition.Suitable pre-mix particles for incorporation of dyes/benefit agents intolaundry care compositions of the invention are described for example inWO 2010/084039, WO 2007/039042, WO 2010/022775, WO 2009/132870, WO2009/087033, WO 2007/006357, WO 2007/039042, WO 2007/096052, WO2011/020991, WO 2006/053598, WO 2003/018740 and WO 2003/018738.

In a second embodiment, the invention provides a method for treatingtextile articles or fabrics. In general, the method comprises the stepsof: (a) providing a laundry care composition as described above; (b)adding the laundry care composition to a liquid medium; and (c) placingthe textile articles in the liquid medium. The method is preferablyperformed under conditions sufficient to convert the compound conformingto a structure selected from the group consisting of Formulae (I)-(XC)from the unconjugated state represented by the structure to a conjugatedstate.

The compositions of this invention, prepared as hereinbefore described,can be used to form aqueous washing/treatment solutions for use in thelaundering/treatment of fabrics. Generally, an effective amount of suchcompositions is added to water, for example in a conventional fabricautomatic washing machine, to form such aqueous laundering solutions.The aqueous washing solution so formed is then contacted, typicallyunder agitation, with the fabrics to be laundered/treated therewith. Aneffective amount of the liquid detergent compositions herein added towater to form aqueous laundering solutions can comprise amountssufficient to form from about 500 to 7,000 ppm of composition in aqueouswashing solution, or from about 1,000 to 3,000 ppm of the detergentcompositions herein will be provided in aqueous washing solution.

Typically, the wash liquor is formed by contacting the laundry carecomposition with wash water in such an amount so that the concentrationof the laundry care composition in the wash liquor is from above 0 g/lto 5 g/l, or from 1 g/l, and to 4.5 g/l, or to 4.0 g/l, or to 3.5 g/l,or to 3.0 g/l, or to 2.5 g/l, or even to 2.0 g/l, or even to 1.5 g/l.The method of laundering fabric or textile may be carried out in atop-loading or front-loading automatic washing machine, or can be usedin a hand-wash laundry application. In these applications, the washliquor formed and concentration of laundry detergent composition in thewash liquor is that of the main wash cycle. Any input of water duringany optional rinsing step(s) is not included when determining the volumeof the wash liquor.

The wash liquor may comprise 40 liters or less of water, or 30 liters orless, or 20 liters or less, or 10 liters or less, or 8 liters or less,or even 6 liters or less of water. The wash liquor may comprise fromabove 0 to 15 liters, or from 2 liters, and to 12 liters, or even to 8liters of water. Typically from 0.01 kg to 2 kg of fabric per liter ofwash liquor is dosed into said wash liquor. Typically from 0.01 kg, orfrom 0.05 kg, or from 0.07 kg, or from 0.10 kg, or from 0.15 kg, or from0.20 kg, or from 0.25 kg fabric per liter of wash liquor is dosed intosaid wash liquor. Optionally, 50 g or less, or 45 g or less, or 40 g orless, or 35 g or less, or 30 g or less, or 25 g or less, or 20 g orless, or even 15 g or less, or even 10 g or less of the composition iscontacted to water to form the wash liquor. Such compositions aretypically employed at concentrations of from about 500 ppm to about15,000 ppm in solution. When the wash solvent is water, the watertemperature typically ranges from about 5° C. to about 90° C. and, whenthe situs comprises a fabric, the water to fabric ratio is typicallyfrom about 1:1 to about 30:1. Typically the wash liquor comprising thelaundry care composition of the invention has a pH of from 3 to 11.5.

In one aspect, such method comprises the steps of optionally washingand/or rinsing said surface or fabric, contacting said surface or fabricwith any composition disclosed in this specification then optionallywashing and/or rinsing said surface or fabric is disclosed, with anoptional drying step.

Drying of such surfaces or fabrics may be accomplished by any one of thecommon means employed either in domestic or industrial settings. Thefabric may comprise any fabric capable of being laundered in normalconsumer or institutional use conditions, and the invention isparticularly suitable for synthetic textiles such as polyester and nylonand especially for treatment of mixed fabrics and/or fibres comprisingsynthetic and cellulosic fabrics and/or fibres. As examples of syntheticfabrics are polyester, nylon, these may be present in mixtures withcellulosic fibres, for example, polycotton fabrics. The solutiontypically has a pH of from 7 to 11, more usually 8 to 10.5. Thecompositions are typically employed at concentrations from 500 ppm to5,000 ppm in solution. The water temperatures typically range from about5° C. to about 90° C. The water to fabric ratio is typically from about1:1 to about 30:1.

The change in color state can occur at any suitable point in the methoddescribe above. For example, the compound can change from the firstcolor state to the second color state while the fabric is beingcontacted with the composition, such as during the wash or rinse cyclesof a laundering process. Alternatively, the compound can undergo thecolor change when the fabric is exposed to heat during the drying stepor to ultraviolet light when the fabric is later exposed to sunlight(e.g., exposure to sunlight from line drying or wearing the fabricoutside).

Example 1

This example demonstrates the production of6-(dimethylamino)-3-[p-(dimethylamino)phenyl]phthalide, which has thefollowing structure:

This compound is a useful intermediate in the production of compoundsthat are suitable for use in the laundry care compositions describedherein.

First, in a 1 L three-neck flask with a condenser, mechanical stirrer,thermal couple, and a N₂ inlet, 74.5 gram of4-dimethylaminobenzaldehyde, 82.5 gram of 3-dimethylaminobenzoic acid,and 250 mL of acetic anhydride were added and heated to reflux for 6hours. The mixture was cooled to below 80° C. 45 mL of water was added,and the contents of the flask were stirred for 2 hours. The contents ofthe flash were then cooled to room temperature, and 250 mL of methanolwas added. While the contents of the flask were stirred, a solid formedwhich was later collected by filtration. The recovered solid product waswashed with methanol, and then dried in a vacuum oven at 60° C.

Example 2

This example demonstrates the production of5-(Dimethylamino)-2-[p-(dimethylamino)benzoyl]benzoic acid, which hasthe following structure:

This compound is a useful intermediate in the production of compoundsthat are suitable for use in the laundry care compositions describedherein.

In a 250 mL three-neck flask with a condenser, mechanical stirrer,thermal couple, and N₂ inlet, 10 gram of6-(dimethylamino)-3-[p-(dimethylamino)phenyl]phthalide and 40 mL of 10%NaOH solution were added. The contents of the flask were heated to 90°C. and stirred for about 1 hour until a clear solution was obtained.Then, 10 grams of sodium m-nitrobenzenesulfonate was added to thesolution. The contents of the reactor were heated to reflux for 15 hoursand then cooled to room temperature. The contents of the flask werefiltered to remove any solid. Then, the filtrate was adjusted to a pH ofabout 4.0 by adding acetic acid. After cooling the contents to roomtemperature, a precipitate formed. The precipitate was collected byfiltration, washed with water, and dried in vacuum at about 60° C.

Example 3

This example demonstrates the production of several compounds that arebelieved to be suitable for use in the laundry care compositionsdescribed herein.

In order to produce each compound, 40 mmol of5-(Dimethylamino)-2-[p-(dimethylamino)benzoyl]benzoic acid, 40 mmol of asubstituted aniline derivative (described below), and 20 mL of aceticanhydride were added to a 250 mL three-neck flask. The contents of theflask were heated to 100° C. and stirred for 5 hours. The resultingcompound was then collected by rotational evaporation.

The substituted aniline derivative used in the reaction described aboveconforms to the following general structure:

R₅ and R₆ are selected from the various groups described above. Table 1shows the structures of specific substituted aniline derivatives used toproduce compounds using the synthetic process described above. Table 2shows the structure of the resulting phtalide compound.

TABLE 1 Structures of substituted aniline derivatives used in thereactions. Sample Structure of substituted aniline derivative 3A

3B

3C

3D

3E

TABLE 2 Structures of resulting phthalide compounds. Sample Structure ofresulting phthalide compound 3A

3B

3C

3D

3E

All references, including publications, patent applications, andpatents, cited herein are hereby incorporated by reference to the sameextent as if each reference were individually and specifically indicatedto be incorporated by reference and were set forth in its entiretyherein.

The use of the terms “a” and “an” and “the” and similar referents in thecontext of describing the subject matter of this application (especiallyin the context of the following claims) are to be construed to coverboth the singular and the plural, unless otherwise indicated herein orclearly contradicted by context. The terms “comprising,” “having,”“including,” and “containing” are to be construed as open-ended terms(i.e., meaning “including, but not limited to,”) unless otherwise noted.Recitation of ranges of values herein are merely intended to serve as ashorthand method of referring individually to each separate valuefalling within the range, unless otherwise indicated herein, and eachseparate value is incorporated into the specification as if it wereindividually recited herein. All methods described herein can beperformed in any suitable order unless otherwise indicated herein orotherwise clearly contradicted by context. The use of any and allexamples, or exemplary language (e.g., “such as”) provided herein, isintended merely to better illuminate the subject matter of theapplication and does not pose a limitation on the scope of the subjectmatter unless otherwise claimed. No language in the specification shouldbe construed as indicating any non-claimed element as essential to thepractice of the subject matter described herein.

Preferred embodiments of the subject matter of this application aredescribed herein, including the best mode known to the inventors forcarrying out the claimed subject matter. Variations of those preferredembodiments may become apparent to those of ordinary skill in the artupon reading the foregoing description. The inventors expect skilledartisans to employ such variations as appropriate, and the inventorsintend for the subject matter described herein to be practiced otherwisethan as specifically described herein. Accordingly, this disclosureincludes all modifications and equivalents of the subject matter recitedin the claims appended hereto as permitted by applicable law. Moreover,any combination of the above-described elements in all possiblevariations thereof is encompassed by the present disclosure unlessotherwise indicated herein or otherwise clearly contradicted by context.

What is claimed is:
 1. A laundry care composition comprising a laundrycare ingredient and at least one compound conforming to the structure ofFormula (I) below

wherein X₁ and X₂ are selected from the group consisting of a carbonatom and a nitrogen atom; a is an integer from 0 to 5, provided a is aninteger from 0 to 4 when one of X₁ and X₂ is a nitrogen atom and a is aninteger from 0 to 3 when both X₁ and X₂ are nitrogen atoms; each R₁ isindependently selected from the group consisting of halogens, a hydroxygroup, a nitro group, alkyl groups, substituted alkyl groups, —S(O)₂OH,—S(O)₂O⁻[M⁺], —C(O)OR₅, —C(O)R₅, —C(O)NR₅R₆, —NC(O)OR₅, —NC(O)SR₅, —OR₅,—NR₅R₆, —S(O)₂R₅, —S(O)₂NR₅R₆, and —P(O)₂R₅; M is a cation; R₅ and R₆are independently selected from the group consisting of hydrogen, alkylgroups, substituted alkyl groups, aryl groups, substituted aryl groups,and R_(a); R₂ and R₃ are independently selected from the groupconsisting of aryl groups, substituted aryl groups, heteroaryl groups,and substituted heteroaryl groups, provided at least one of R₂ and R₃ isa heteroaryl group or a substituted heteroaryl group when both X₁ and X₂are carbon atoms; L₁ is selected from the group consisting of hydrogen,halogens, a hydroxy group, a cyano group, and —OR₈; R₈ is selected fromthe group consisting of alkyl groups and substituted alkyl groups;wherein R_(a) is selected from the group consisting of—R_(x)—O—R_(y)—R_(z) and —R_(y)—R_(z); R_(x) is selected from the groupconsisting of alkanediyl groups and arenediyl groups; R_(z) is selectedfrom the group consisting of hydrogen, alkyl groups, substituted alkylgroups, acyl groups, and R_(b); R_(b) is a monovalent group conformingto the structure of Formula (I); and R_(y) is a divalent substituentselected from the group consisting of: (i) divalent substituentscomprising two or more divalent repeating units independently selectedfrom repeating units conforming to the structure of Formula (C)

wherein R₁₀₁ and R₁₀₂ are independently selected from the groupconsisting of hydrogen, alkyl, hydroxyalkyl, aryl, alkoxyalkyl, andaryloxyalkyl; (ii) divalent substituents conforming to the structure ofFormula (CX)

wherein R₁₁₁ and R₁₁₂ are independently selected from the groupconsisting of hydrogen, hydroxyl, and C₁-C₁₀ alkyl, aa is an integerfrom 1 to 12, and bb is an integer greater than or equal to 1 (e.g.,from 1 to 100); (iii) divalent substituents conforming to the structureof Formula (CXX)

wherein R₁₂₁ and R₁₂₂ are independently selected from the groupconsisting of hydrogen, hydroxyl, and C₁-C₁₀ alkyl, cc is an integerfrom 1 to 12, and dd is an integer greater than or equal to 1 (e.g.,from 1 to 100); (iv) divalent substituents conforming to the structureof Formula (CXXX)

wherein R₁₃₁, R₁₃₂, and R₁₃₃ are independently selected from alkyl andhydroxyalkyl, and ee is an integer greater than or equal to 1 (e.g.,from 1 to 100); (v) divalent substituents conforming to the structure ofFormula (CXL)

wherein each R₁₄₁ is independently selected from the group consisting ofhydrogen and alkylamine groups, and ff is an integer greater than orequal to 1 (e.g., from 1 to 100); (vi) divalent substituents conformingto the structure of Formula (CL)

wherein gg is an integer greater than or equal to 1 (e.g., from 1 to100); (vii) divalent substituents conforming to the structure of Formula(CLX)

wherein each R₁₆₁ is independently selected from the group consisting ofhydrogen and methyl, and hh is an integer greater than or equal to 1(e.g., from 1 to 100); (viii) divalent substituents conforming to thestructure of Formula (CLXX)

wherein each R₁₇₁, R₁₇₂, and R₁₇₃ is independently selected from thegroup consisting of hydrogen and —CH₂CO₂H, and jj is an integer greaterthan or equal to 1 (e.g., from 1 to 100); and (ix) divalent substituentscomprising two or more substituents selected from the group consistingof substituents conforming to a structure of Formula (C), (CX), (CXX),(CXXX), (CXL), (CL), (CLX), or (CLXX).
 2. The laundry care compositionof claim 1, wherein R_(y) is a divalent substituent conforming to astructure selected from the group consisting of Formulae (CA), (CB), and(CC)

wherein ff, gg, and hh are selected from the group consisting of zeroand positive integers, and the sum of ff, gg, and hh is 2 or more. 3.The laundry care composition of claim 1, wherein the compound conformingto the structure of Formulae (I) comprises at least one R_(a) group. 4.A method for treating textile articles, the method comprising the stepsof: (a) providing the laundry care composition of claim 1; (b) addingthe laundry care composition to a liquid medium; and (c) placing thetextile articles in the liquid medium.
 5. The method of claim 4, whereinthe method is performed under conditions sufficient to convert thecompound conforming to the structure of Formulae (I) from anunconjugated form represented by the structure to a conjugated form. 6.The laundry care composition of claim 1, wherein R₂ and R₃ are selectedfrom the group consisting of aryl groups, substituted aryl groups,heteroaryl groups, and substituted heteroaryl groups conforming to astructure of Formula (IA)— (IF) below

wherein R₉ is selected from the group consisting of alkyl groups,substituted alkyl groups, aryl groups, substituted aryl groups,heteroaryl groups, substituted heteroaryl groups, a cyano group,halogens, —S(O)₂OH, —S(O)₂NR₅R₆, —C(O)OH, and —C(O)OR₅, provided two ormore adjacent R₉ groups can be combined to form a fused ring structure;X₃, X₄, X₅, and X₆ are selected from the group consisting of a carbonatom and a nitrogen atom, provided (1) at least one of X₃, X₄, X₅, andX₆ is a nitrogen atom, (2) when X₄ is a nitrogen atom, then X₃ and X₅are both carbon atoms and (3) when X₃ is a nitrogen atom, then X₄ is acarbon atom; the variables za and zb are independently selected from thegroup consisting of integers from 0 to 5, with the sum of za and zbbeing an integer from 0 to 5; the variables zc and zd are independentlyselected from the group consisting of integers from 0 to 3; thevariables ze and zf are independently selected from the group consistingof integers from 0 to 4, with the sum of ze and zf being less than orequal to 5-N, where N is equal to the number of nitrogen atoms in thearomatic ring.